EP1247568A1 - Microcapsules (XIII) - Google Patents
Microcapsules (XIII) Download PDFInfo
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- EP1247568A1 EP1247568A1 EP01108374A EP01108374A EP1247568A1 EP 1247568 A1 EP1247568 A1 EP 1247568A1 EP 01108374 A EP01108374 A EP 01108374A EP 01108374 A EP01108374 A EP 01108374A EP 1247568 A1 EP1247568 A1 EP 1247568A1
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- EP
- European Patent Office
- Prior art keywords
- microcapsules
- acid
- aqueous
- matrix
- meth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/12—Processes in which the treating agent is incorporated in microcapsules
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/11—Encapsulated compositions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/10—Complex coacervation, i.e. interaction of oppositely charged particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/20—After-treatment of capsule walls, e.g. hardening
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
Definitions
- the invention is in the fields of cosmetics or pharmacy as well as textile finishing agents and relates to new microcapsules, a process for their production and their use in cosmetics and textile technology.
- microcapsule describes spherical aggregates with a Understand diameters in the range of about 0.1 to about 5 mm, the at least one contain solid or liquid core, which is enclosed by at least one continuous shell is. More specifically, they are coated with film-forming polymers finely dispersed liquid or solid phases, in the production of which the polymers change after emulsification and coacervation or interfacial polymerization on the material to be encased knock down. Another process involves melting waxes in a matrix added (“microsponge”), which as microparticles additionally with film-forming polymers can be enveloped. The microscopic capsules can be dried like powder.
- multinuclear aggregates also called microspheres, known that contain two or more cores distributed in the continuous shell material.
- Monocore or multi-core microcapsules can also have an additional second, third etc. envelope be enclosed.
- the shell can be natural, semi-synthetic or synthetic Materials exist.
- wrapping materials are, for example, gum arabic, Agar-agar, agarose, maltodextrins, alginic acid or their salts, e.g.
- Semi-synthetic shell materials include chemically modified ones Celluloses, especially cellulose esters and ethers, e.g. Cellulose acetate, ethyl cellulose, Hydroxypropyl cellulose, hydroxypropyl methyl cellulose and carboxymethyl cellulose, as well Starch derivatives, especially starch ethers and esters.
- There are synthetic wrapping materials for example polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinyl pyrrolidone.
- microcapsules of the prior art are the following commercial products (in each case the shell material is given in brackets): Hallcrest microcapsules (gelatin, gum arabic), Coletica Thalaspheres (maritime collagen), Lipotec millicapsules (alginic acid, agar), induchem unispheres (lactose , microcrystalline cellulose, hydroxypropylmethyl cellulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified agar) and Kuhs Probiol Nanospheres (phospholipids).
- the prior art microcapsules are not entirely satisfactory.
- the capsules turn out to be too soft and especially too hot easily deformable, so that the active ingredient is released too quickly.
- the object of the present invention was therefore to provide microcapsules with the to provide known advantageous properties, but which have a harder Shell and improved resistance to water and heat.
- the anionic polymers or polyacrylates react with the chitosan to an inner envelope membrane that includes the active ingredient.
- the second step is to respond then unreacted amino groups of the chitosan with the polyacrylates or the others anionic polymers forming the outer shell, so that a capsule with two shells are created.
- These new microcapsules have improved mechanical ones Characteristics. They are less easily washed out by water, are more resilient and soften even slowly at 40 ° C, which together results in a significantly more delayed Release of the encapsulated active ingredients results.
- active ingredients that are included in the new microcapsules are in itself critical. They are preferably substances that only result from mechanical destruction the microcapsules are released. In these cases, the microcapsules do the job to, the contact between the external environment and the active ingredient and thus a chemical reaction or to prevent degradation. It may be that those enclosed in the capsule Substances should not be released at all and only serve the purpose to give the preparation an aesthetic appearance; this is often the case for dyes too. It is of course clear that these types of use also exist side by side can. In particular, it is possible, for example, a fragrance for later release to encapsulate together with a color pigment, which makes the capsule a special one Gives appearance.
- active ingredients such as those in the cosmetic and pharmaceutical field Preparations are used are surfactants, cosmetic oils, pearlescent waxes, Stabilizers, biogenic agents, vitamins, deodorants, antiperspirants, antidandruff agents, UV light protection factors, antioxidants, preservatives, insect repellents, Self - tanners, typrosin inhibitors (depigmenting agents), perfume oils, flavors and Dyes.
- Anionic, nonionic, cationic and / or amphoteric or amphoteric surfactants may be present as surface-active substances, the proportion of which in the compositions is usually about 1 to 70, preferably 5 to 50 and in particular 10 to 30% by weight.
- anionic surfactants are soaps, alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, mono-ether ether sulfate, (hydroxymethoglysulfate), monohydric ether sulfate dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and salts thereof, fatty acid taurides, N-acylamino acids such as acyl lactylates, acy
- nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, optionally partially oxidized alk (en) yl oligoglycosides or especially glucoramide-acid-based vegetable derivatives, , Polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides.
- nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
- cationic surfactants are quaternary ammonium compounds, such as, for example, dimethyldistearylammonium chloride, and esterquats, in particular quaternized fatty acid trialkanolamine ester salts.
- amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The surfactants mentioned are exclusively known compounds.
- Typical examples of particularly suitable mild, ie particularly skin-compatible, surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid taurides, fatty acid glutamates, ⁇ -olefin sulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines, amphoacetals and / or protein fatty acid condensates, preferably based on wheat proteins.
- Cosmetic oils include, for example, Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C 6 -C 22 fatty acids with linear C 6 -C 22 fatty alcohols, esters of branched C 6 -C 13 - carboxylic acids with linear C 6 -C 22 -fatty alcohols, such as myristyl myristate, myristyl palmitate, myristyl stearate, Myristylisostearat, myristyl, Myristylbehenat, Myristylerucat, cetyl myristate, cetyl palmitate, cetyl stearate, Cetylisostearat, cetyl oleate, cetyl behenate, Cetylerucat, Stearylmyristat, stearyl palmitate, stearyl stearate, Stearylisostearat, stearyl oleate , stearyl, Steary
- esters of linear C 6 -C 22 fatty acids with branched alcohols in particular 2-ethylhexanol
- esters of linear and / or branched fatty acids are also suitable polyhydric alcohols (such as propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, triglycerides based on C 6 -C 10 fatty acids, liquid mono- / di- / trl glyceride mixtures based on C 6 -C 18 fatty acids, esters of C 6 -C 22 fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, especially benzoic acid, esters of C 2 -C 12 dicarboxylic acids with linear or branched alcohols with 1 to 22 carbon atoms or polyols with 2 to 10
- Finsolv® TN linear or branched, symmetrical or unsymmetrical dialkyl ethers with 6 to 22 carbon atoms per alkyl group, ring opening products of epoxidized fatty acid esters with polyols, silicone oils and / or aliphatic or naphthenic Hydrocarbons, such as, for example, squalane, squalene or dialkylcyclohexanes.
- Pearlescent waxes that can be used are, for example: alkylene glycol esters, especially ethylene glycol distearate; Fatty acid alkanolamides, especially coconut fatty acid diethanolamide; partial glycerides, especially stearic acid monoglyceride; Esters of polyvalent, if necessary hydroxy substituted carboxylic acids with fatty alcohols with 6 to 22 carbon atoms, especially long chain esters of tartaric acid; Fatty substances, such as fatty alcohols, Fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, totaling at least 24 Have carbon atoms, especially lauron and distearyl ether; Fatty acids such as stearic acid, Hydroxystearic acid or behenic acid, ring opening products of olefin epoxides with 12 to 22 carbon atoms with fatty alcohols with 12 to 22 carbon atoms and / or polyols with 2 to 15 carbon atoms and 2 to 10 hydroxyl groups
- Metal salts of fatty acids such as e.g. Magnesium, aluminum and / or Zinc stearate or ricinoleate can be used.
- biogenic active ingredients examples include tocopherol, tocopherol acetate, tocopherol palmitate, Ascorbic acid, deoxyribonucleic acid, retinol, retinyl palmitate, bisabolol, Allantoin, phytantriol, panthenol, menthol, tea tree oil, AHA acids, kojic acid, amino acids, Ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes to understand.
- deodorants counteract body odors, mask them or eliminate them. Body odors arise from the action of skin bacteria on apocrine sweat, forming unpleasant smelling breakdown products become. Accordingly, deodorants contain active ingredients that are considered germ-inhibiting Agents, enzyme inhibitors, odor absorbers or odor maskers act.
- Esterase inhibitors are suitable as enzyme inhibitors. This is about it is preferably trialkyl citrates such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, Tributyl citrate and especially triethyl citrate (Hydagen® CAT, Henkel KGaA, Düsseldorf / FRG).
- the substances inhibit enzyme activity and thereby reduce odor.
- esterase inhibitors include sterolsulfates or phosphates, such as lanosterol, cholesterol, campesterol, Stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and their esters, such as for example glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, Monoethyl adipate, diethyl adipate, malonic acid and diethyl malonate, Hydroxycarboxylic acids and their esters such as citric acid, Malic acid, tartaric acid or tartaric acid diethyl ester, as well as zinc glycinate.
- sterolsulfates or phosphates such as lanosterol, cholesterol, campesterol, Stigmasterol and sitosterol sulfate or phosphate
- dicarboxylic acids and their esters such as for example glutaric acid, glutaric acid monoethyl
- Substances which absorb odor-forming compounds are suitable as odor absorbers and can hold on to a large extent. They reduce the partial pressure of the individual components and thus reduce their speed of propagation. It is important that Perfumes must remain unaffected. Odor absorbers have no effectiveness against bacteria. For example, they contain a complex zinc salt as the main component the ricinoleic acid or special, largely odorless fragrances that the Are known in the art as "fixators" such. B. extracts of Labdanum or Styrax or certain abietic acid derivatives. Fragrances or act as odor maskers Perfume oils that, in addition to their function as odor maskers, deodorants their give each fragrance note. Mixtures may be mentioned as perfume oils from natural and synthetic fragrances.
- Natural fragrances are extracts of flowers, stems and leaves, fruits, fruit peels, roots, woods, herbs and grasses, needles and twigs as well as resins and balms. Furthermore come animal Raw materials in question, such as civet and castoreum.
- Typical synthetic Fragrance compounds are products of the ester, ether, aldehyde, ketone, Alcohols and hydrocarbons. Fragrance compounds of the ester type are e.g.
- ethers include, for example, benzyl ethyl ether, the aldehydes e.g.
- the linear Alkanals with 8 to 18 carbon atoms citral, citronellal, citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g. the Jonone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, isoeugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons belong mainly to the terpenes and balms. However, mixtures are preferred different fragrances are used, which together produce an appealing fragrance.
- perfume oils e.g. Sage oil, chamomile oil, clove oil, lemon balm oil, Mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, Galbanum oil, Labdanum oil and Lavandin oil.
- Antiperspirants reduce by affecting the activity of the eccrine sweat glands sweat, and thus act armpit wetness and body odor opposite.
- Suitable as astringent antiperspirant active ingredients are above all Salts of aluminum, zirconium or zinc.
- Such suitable antiperspirant active ingredients are e.g. Aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, Aluminum sesquichlorohydrate and their complex compounds e.g. B. with 1,2-propylene glycol.
- oil-soluble and water-soluble oils commonly used in antiperspirants Aids may be included in smaller quantities.
- oil-soluble aids can e.g. anti-inflammatory, skin-protecting or fragrant essential oils, synthetic skin-protecting agents and / or oil-soluble perfume oils.
- Climbazole, octopirox, ketoconazole and zinc pyrethione can be used as antidandruff agents be used.
- UV light protection factors are, for example, liquid or crystalline at room temperature present organic substances (light protection filters) that are able to understand are to absorb ultraviolet rays and the absorbed energy in the form longer-wave radiation, e.g. To give off heat again.
- UVB filters can be oil-soluble or be water soluble.
- oil-soluble substances e.g. to name: 3-benzylidene camphor or 3-benzylidene norcampher and its derivatives, e.g.
- Possible water-soluble substances are: 2-phenylbenzimidazole-5-sulfonic acid and their alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and their salts; Sulfonic acid derivatives of 3-benzylidene camphers, e.g. 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.
- UV-A filter derivatives of benzoylmethane are particularly suitable, such as 1- (4'-tert-butyl-phenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl-4'-methoxydibenzoyl-methane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and also E-namin compounds, as described in DE 19712033 A1 (BASF).
- the UV-A and UVB filters can of course also be used in mixtures.
- insoluble light protection pigments for this purpose, namely finely dispersed metal oxides or salts in question.
- Metal oxides are in particular zinc oxide and titanium dioxide and also oxides of iron, Zirconium, silicon, manganese, aluminum and cerium and their mixtures.
- Silicates (talc) barium sulfate or zinc stearate can be used.
- the oxides and Salts are in the form of pigments for skin-care and skin-protecting emulsions and used decorative cosmetics.
- the particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular have between 15 and 30 nm.
- the pigments can also be surface treated, i.e. are hydrophilized or hydrophobized.
- Typical examples are coated titanium dioxides, e.g. Titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck).
- the main hydrophobic coating agents are Silicones and especially trialkoxyoctylsilanes or simethicones in question.
- sunscreens so-called micro- or nanopigments are preferred as encapsulated active ingredients used.
- Micronized zinc oxide is preferably used.
- Further Suitable UV light protection filters are in the overview by P.Finkel in S ⁇ FW-Journal 122, 543 (1996).
- secondary light stabilizers of the antioxidant type can also be used, which interrupt the photochemical reaction chain which is triggered when UV radiation penetrates the skin.
- Typical examples are amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (e.g. anserine) , Carotenoids, carotenes (e.g.
- ⁇ -carotene, ⁇ -carotene, lycopene and their derivatives, chlorogenic acid and their derivatives, lipoic acid and their derivatives (e.g. dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (e.g.
- thioredoxin glutathione, cysteine, cystine, Cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, ⁇ -linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate , Distearylthiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (e.g.
- buthioninsulfoximines homocysteine sulfoximine, butioninsulfones, penta-, hexa-, heptathioninsulfoximine) in very low ver inert dosages (e.g. pmol to ⁇ mol / kg), (metal) chelators (e.g. ⁇ -hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), ⁇ -hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, Biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g.
- metal chelators e.g. ⁇ -hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin
- ⁇ -hydroxy acids e.g. citric acid, lactic acid, malic acid
- humic acid bile acid
- ⁇ -linolenic acid linoleic acid, oleic acid
- folic acid and their derivatives ubiquinone and ubiquinol and their derivatives
- vitamin C and derivatives e.g. ascorbyl palmitate, Mg-ascorbyl phosphate, ascorbyl acetate
- Tocopherols and derivatives e.g.
- vitamin E acetate
- vitamin A and derivatives vitamin A palmitate
- Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, Parabens, pentanediol or sorbic acid as well as those in Appendix 6, Parts A and B further cosmetic classes listed in the Cosmetics Ordinance.
- insect repellents come N, N-diethyl-m-toluamide, 1,2-pentanediol or ethyl butylacetylaminopropionate in question, dihydroxyacetone is suitable as a self-tanner.
- tyrosine inhibitors the Prevent the formation of melanin and find application in depigmenting agents, arbutin, kojic acid, coumaric acid and ascorbic acid (vitamin C) in question.
- Perfume oils include mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers (lily, lavender, roses, jasmine, neroli, Ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, Coriander, caraway, juniper), fruit peels (bergamot, lemon, oranges), roots (Macis, Angelica, Celery, Cardamom, Costus, Iris, Calmus), Woods (Pine, Sandal, Guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, Thyme), needles and twigs (spruce, fir, pine, mountain pine), resins and balsams (Galbanum, Elemi, Benzoe, Myrrh, Olibanum, Opoponax).
- Typical synthetic Fragrance compounds are products of the ester, ether, aldehyde, ketone, and alcohol type and hydrocarbons. Fragrance compounds of the ester type are e.g.
- ethers include, for example, benzyl ethyl ether, the aldehydes e.g.
- the linear Alkanals with 8 to 18 carbon atoms citral, citronellal, citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g. the Jonone, ⁇ -isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, Eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons belong mainly to the terpenes and balms.
- fragrance oils are used, which together make an appealing Generate fragrance.
- perfume oils e.g. Sage oil, chamomile oil, Clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, Vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil.
- Suitable dyes are those which are suitable and approved for cosmetic purposes are used, such as those used in the publication "Cosmetic Colorants” the dye commission of the German Research Foundation, Verlag Chemie, Weinheim, 1984, p.81-106 are compiled. These agents can too Contained in the capsules only for aesthetic reasons and not for one controlled release.
- a second area of application for the new microcapsules is in the finishing of textiles.
- the particular advantage here is that the capsules at significantly higher temperatures soften and do not release the flame retardant too early.
- suitable ones Active substances are all types of flame retardants, i.e. metal oxides, e.g. magnesium oxide, Calcium oxide, aluminum oxide or antimony (III) oxide, organic halides, such as e.g. Tetrabromobisphenol A or decabromodiphenyl oxide and in particular organic phosphorus compounds, such as. Triphenyl phosphate (TPP), tricresyl phosphate (TCP), cresyl diphenyl phosphate (CDP) or tetraphenyl diphosphate.
- the agents are preferably with particle sizes used in the range of 0.1 to 5 mm.
- the active ingredients are used in such quantities that their share in the finished ones Microcapsules usually 1 to 25, preferably 5 to 15 and in particular 8 to 10 % By weight.
- the alginates and / or carboxymethyl celluloses have the task of forming the inner membranes with the chitosans.
- Salts of alginic acid are preferably suitable for this purpose.
- Alginic acid is a mixture of carboxyl-containing polysaccharides with the following idealized monomer unit: The average molecular weight of the alginic acids or alginates is in the range from 150,000 to 250,000.
- Salts of alginic acid are to be understood as meaning both their complete and their partial neutralization products, in particular the alkali metal salts and among these preferably the sodium alginate (“algin”) and the ammonium and alkaline earth metal salts.
- Mixed alginates such as sodium / magnesium or sodium / calcium alginates, are particularly preferred.
- carboxymethyl celluloses are also suitable for this purpose, in particular those which are already commercially available as customary detergent additives.
- the alginates and / or carboxymethyl celluloses are used in amounts such that their proportion in the finished microcapsules is 20 to 40, preferably 25 to 35 and in particular around 30% by weight.
- the adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols or with castor oil are known, commercially available products. These are mixtures of homologs whose average degree of alkoxylation is the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate, with which the addition reaction is carried out.
- C 12/18 fatty acid monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE 2024051 PS as refatting agents for cosmetic preparations.
- Alkyl and / or alkenyl oligoglycosides their preparation and their use are out known in the art. They are manufactured in particular through implementation of glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms.
- Glycosidrestes applies that both monoglycosides in which a cyclic sugar residue is glycosidically bound to the fatty alcohol, as well as oligomeric Glycosides with a degree of oligomerization of up to preferably about 8 are suitable.
- the Degree of oligomerization is a statistical mean, one for such technical Products based on the usual homolog distribution.
- Typical examples of suitable partial glycerides are hydroxystearic acid monoglyceride, Hydroxystearic acid diglyceride, isostearic acid monoglyceride, isostearic acid diglyceride, Oleic acid monoglyceride, oleic acid diglyceride, ricinoleic acid moglyceride, ricinoleic acid diglyceride, Linoleic acid monoglyceride, linoleic acid diglyceride, linolenic acid monoglyceride, linolenic acid diglyceride, Erucic acid monoglyceride, erucic acid diglyceride, tartaric acid monoglyceride, Tartaric acid diglyceride, citric acid monoglyceride, citric diglyceride, malic acid monoglyceride, Malic acid diglyceride and their technical mixtures, the subordinate may still contain small amounts of triglyceride from the manufacturing process. Likewise Addition products of
- polyglycerol esters are polyglyceryl-2 dipolyhydroxystearates (Dehymuls® PGPH), polyglycerol-3-diisostearate (Lameform® TGI), polyglyceryl-4 Isostearate (Isolan® GI 34), polyglyceryl-3 oleates, diisostearoyl polyglyceryl-3 Diisostearate (Isolan® PDI), polyglyceryl-3 methylglucose distearate (Tego Care® 450), Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010 / 90), Polyglyceryl-3 Cetyl Ether (Chimexane® NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and Polyglyceryl Polyricinoleate (Admul® WOL 1403) Polyglyceryl Dimerate is
- polystyrene resin examples include the mono-, di- and optionally reacted with 1 to 30 mol ethylene oxide Triester of trimethylolpropane or pentaerythritol with lauric acid, coconut fatty acid, Tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like.
- Typical anionic emulsifiers are aliphatic fatty acids with 12 to 22 carbon atoms, such as palmitic acid, stearic acid or behenic acid, and dicarboxylic acids with 12 to 22 carbon atoms, such as azelaic acid or Sebacic acid.
- Zwitterionic surfactants can also be used as emulsifiers.
- Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule.
- Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example coconut acylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxylm -hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate.
- betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example
- Suitable emulsifiers are ampholytic surfactants.
- Ampholytic surfactants are surface-active compounds which, in addition to a C 8/18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO 3 H group in the molecule and are capable of forming internal salts.
- ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 carbon atoms in the alkyl group.
- Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C 12/18 acylsarcosine.
- cationic surfactants are also suitable as emulsifiers, those of the esterquat type, preferably methylquaternized difatty acid triethanolamine ester salts, being particularly preferred.
- the emulsifiers are used in such quantities that their share in the produce microcapsules 0.1 to 5, preferably 0.25 to 2 and in particular 0.5 to 1% by weight is.
- Chitosans are biopolymers and belong to the group of hydrocolloids. From a chemical point of view, these are partially deacetylated chitins of different molecular weights that contain the following - idealized - monomer unit:
- chitosans are cationic biopolymers under these conditions.
- the positively charged chitosans can interact with oppositely charged surfaces and are therefore used in cosmetic hair and body care products and pharmaceuticals Preparations used (cf. Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A6, Weinheim, Verlag Chemie, 1986, pp. 231-232).
- Overviews on this topic are also available, for example, from B. Gesslein et al. in HAPPI 27 , 57 (1990), O. Skaugrud in Drug Cosm. Ind. 148: 24 (1991) and E. Onsoyen et al.
- chitosans is based on chitin, preferably the shell remains of crustaceans, which are available in large quantities as cheap raw materials.
- the chitin is used in a process that was first developed by Hackmann et al. has been described, usually first deproteinized by adding bases, demineralized by adding mineral acids and finally deacetylated by adding strong bases, it being possible for the molecular weights to be distributed over a broad spectrum.
- Appropriate methods are, for example, made from Makromol. Chem. 177 , 3589 (1976) or French patent application FR 2701266 A.
- Such types are preferably used as are disclosed in German patent applications DE 4442987 A1 and DE 19537001 A1 (Henkel) and which have an average molecular weight of 10,000 to 500,000 or 800,000 to 1,200,000 Daltons and / or a Brookfield viscosity ( 1% by weight in glycolic acid) below 5000 mPas, a degree of deacetylation in the range from 80 to 88% and an ash content of less than 0.3% by weight.
- the chitosans are generally used in the form of their salts, preferably as glycolates. As a rule, the chitosans are used in amounts such that their share in the finished microcapsules is 5 to 30, preferably 10 to 25 and in particular 15 to 20% by weight.
- homo- and copolymers of acrylic and / or methacrylic acid are suitable which, for example, have a molecular weight of 1,000 to 200,000, preferably 5,000 to 100,000 and in particular 10,000 to 50,000 Daltons and are optionally crosslinked.
- suitable commercial products are the Carbopole® and Pemulen types from Goodrich, Synthalene® from Sigma, Keltrol types from Kelco, Sepigel types from Seppic and Salcare types from Allied Colloids. It is particularly preferred to use the Carbopol® ETD 2020 product from Goodrich, a C 10 -C 30 alkyl-crosslinked polyacrylate.
- the poly (meth) acrylates are used in amounts such that their proportion in the finished microcapsules is 5 to 30, preferably 10 to 25 and in particular 15 to 20% by weight.
- a first aqueous solution is usually first prepared Carboxymethyl cellulose solution, which further additives, e.g. preservative and may contain antioxidants and preferably acidic, for example to a pH is set in the range from 2 to 5.
- an aqueous solution or dispersion of the active ingredient in both preparations - or even in one of them - Emulsifiers, which have the functions, can be contained in the following mixture the formation of the emulsion, which is usually an O / W emulsion, to promote.
- This emulsion - also known as the matrix - is now added dropwise and brought into contact with the aqueous solution of the chitosan salt under strong shear, forming the inner shell and encapsulating the active ingredient. Then the aqueous preparation with a poly (meth) acrylate solution, the free amine groups of the chitosan then react with the anionic groups of the polymer, whereby then the outer shell is molded.
- the poly (meth) acrylates can also be used in the first step is to form the inner shell and the alginates or carboxymethyl cellulose then be used to form the outer shell. This essentially requires only the molar exchange of the two types of polymer. Basically, it is further possible, the resulting microcapsules with a double shell again with aqueous Add chitosan solution to make a third shell.
- microcapsules for the production of cosmetic or pharmaceutical preparations as well as textile fabrics, such as yarns, fibers or corresponding end products, which the capsules in quantities from 0.1 to 15, preferably 1 to 10 and in particular 3 to 8% by weight.
- microcapsules according to the invention can be used for the production of cosmetic and / or pharmaceutical preparations, such as hair shampoos, hair lotions, Bubble baths, shower baths, creams, gels, lotions, alcoholic and aqueous / alcoholic Solutions, emulsions, wax / fat masses, stick preparations, powders or Serve ointments.
- cosmetic and / or pharmaceutical preparations such as hair shampoos, hair lotions, Bubble baths, shower baths, creams, gels, lotions, alcoholic and aqueous / alcoholic Solutions, emulsions, wax / fat masses, stick preparations, powders or Serve ointments.
- These agents can also be used as further auxiliaries and additives, mild surfactants, Oil bodies, emulsifiers, pearlescent waxes, consistency agents, thickeners, superfatting agents, Stabilizers, polymers, silicone compounds, fats, waxes, lecithins, Phospholipids, biogenic agents, UV light protection factors, antioxidants, deodorants, Antiperspirants, antidandruff agents, film formers, swelling agents, insect repellents, Self-tanners, tyrosine inhibitors (depigmenting agents), hydrotropes, solubilizers, Contain preservatives, perfume oils, dyes and the like.
- mild surfactants Oil bodies, emulsifiers, pearlescent waxes, consistency agents, thickeners, superfatting agents, Stabilizers, polymers, silicone compounds, fats, waxes, lecithins, Phospholipids, biogenic agents, UV light protection factors, antioxidants, deodorants, Antiperspirants, antid
- microcapsules according to the invention can be used analogously to natural keratin fibers also serve to finish textiles, although the focus here is on improvement of the flame retardant.
- the yarns can be finished in the same way by using the microcapsules, for example, as components of winding oils or spin fiber preparations applies.
- the microcapsules are suitable for equipping everyone textile fabrics.
- the microcapsules also contain fat-soluble dyes, such as for example beta-carotenes or tocopherols, which can then serve as indicators for that the capsules have been absorbed by the tissue.
- Example 1 In a first reaction vessel, 0.5% by weight of preservative (Phenonip®) and 25% by weight of carboxymethyl cellulose were dispersed in water and adjusted to a pH of 3.5. A mixture of 10% by weight retinol, 0.25% by weight sorbitan monolaurate + 20EO (Eumulgin® SML20), 0.25% by weight sorbitan monooleate (Dehymuls® SMO) and 1% by weight was mixed in a second vessel. BHT produced and added to the first mixture, whereby an O / W emulsion was formed.
- a 20% by weight aqueous solution of chitosan glycolate (Hydagen® CMF) was added dropwise to the emulsion with stirring, a first capsule shell being formed by reaction of the chitosan with the carboxymethyl cellulose.
- a 3% by weight polyacrylate solution (Carbopol® ETD 2020, from Goodrich) was then prepared and added in an amount of 20% by weight to the preparation with the first microcapsules, the reaction of the polyacrylate with the free amino groups of the Chitosans forms a second shell.
- the microcapsule content of the preparation was approx. 80% by weight
- Example 2 In a first reaction vessel, 0.5% by weight of preservative (Phenonip®) and 25% by weight of sodium alginate were dispersed in water and adjusted to a pH of 3.5. A mixture of 10% by weight panthenol, 20% by weight sorbitan monolaurate + 20EO (Eumulgin® SML20), 0.25% by weight cetearyl glucosides and 1% by weight BHT and the first mixture was prepared in a second vessel added, resulting in an O / W emulsion.
- a 20% by weight aqueous solution of chitosan glycolate (Hydagen® CMF) was added dropwise to the emulsion with stirring, a first capsule shell being formed by reaction of the chitosan with the carboxymethyl cellulose.
- a 3% by weight polyacrylate solution (Carbopol® ETD 2020, from Goodrich) was then prepared and added in an amount of 20% by weight to the preparation with the first microcapsules, the reaction of the polyacrylate with the free amino groups of the Chitosans forms a second shell.
- the microcapsule content of the preparation was approx. 80% by weight
- Example 3 In a first reaction vessel, 0.5% by weight of preservative (Phenonip®) and 25% by weight of polyacrylate (Carbopol® ETD 2020, from Goodrich) were dispersed in water and brought to a pH of 3.5 set. A mixture of 10% by weight retinol, 0.25% by weight sorbitan monolaurate + 20EO (Eumulgin® SML20), 0.25% by weight sorbitan monooleate (Dehymuls® SMO) and 1% by weight was mixed in a second vessel. BHT produced and added to the first mixture, whereby an O / W emulsion was formed.
- preservative Phonip®
- Carbopol® ETD 2020 polyacrylate
- a 20% by weight aqueous solution of chitosan glycolate (Hydagen® CMF) was added dropwise to the emulsion with stirring, a first capsule shell being formed by reaction of the chitosan with the polyacrylate.
- a 1% by weight carboxymethyl cellulose solution was then prepared and added in an amount of 20% by weight to the preparation with the first microcapsules, a second shell being formed by reaction of the CMC with the free amino groups of the chitosan.
- the microcapsule content of the preparation was approx. 80% by weight
- Formulation examples can be found in Table 1 below.
- Examples of cosmetic preparations water, preservative ad 100 wt .-%) Composition (INCI) 1 2 3 4 5 6 7 8th 9 10 Texapon® NSO Sodium Laureth Sulfate - - - - - - 38.0 38.0 25.0 - Texapon ® SB 3 Disodium Laureth Sutfosuccinate - - - - - - - - 10.0 - Plantacare® 818 Coco Glucosides - - - - - - 7.0 7.0 6.0 - Plantacare® PS 10 Sodium Laureth Sulfate (and) Coco Glucosides - - - - - - - - 16.0 Dehyton® PK 45 Cocamidopropyl Betaine - - - - - - - - - - - - 10.0 - Dehyquart® A Cetrimoni
- composition (INCI) 21 22 23 24 25 26 27 28 29 30 Texapon® NSO Sodium Laureth Sulfate - 30.0 30.0 - 25.0 - - - - - Plantacare® 818 Coco Glucosides - 10.0 - - 20.0 - - - - - Plantacare® PS 10 Sodium Laureth Sulfate (and) Coco Glucosides 22.0 - 5.0 22.0 - - - - - - Dehyton® PK 45 Cocamidopropyl Betaine 15.0 10.0 15.0 15.0 20.0 - - - - - - Emulgade® SE Glyceryl Sterate (and) Ceteareth 12/20 (and) Cetearyl Alcohol (and) Cetyl Palmitate - - - - - 5.0 4.0 - - Eumulgin® B1 Ceteareth-12 - - - - - - - 1.0 - - Lame
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Abstract
Description
Die Erfindung befindet sich auf den Gebieten der Kosmetik bzw. Pharmazie sowie der Textilausrüstungsmittel und betrifft neue Mikrokapseln, ein Verfahren zu deren Herstellung sowie deren Verwendung in der Kosmetik und Textiltechnik.The invention is in the fields of cosmetics or pharmacy as well as textile finishing agents and relates to new microcapsules, a process for their production and their use in cosmetics and textile technology.
Unter dem Begriff "Mikrokapsel" werden vom Fachmann sphärische Aggregate mit einem Durchmesser im Bereich von etwa 0,1 bis etwa 5 mm verstanden, die mindestens einen festen oder flüssigen Kern enthalten, der von mindestens einer kontinuierlichen Hülle umschlossen ist. Genauer gesagt handelt es sich um mit filmbildenden Polymeren umhüllte feindisperse flüssige oder feste Phasen, bei deren Herstellung sich die Polymere nach Emulgierung und Koazervation oder Grenzflächenpolymerisation auf dem einzuhüllenden Material niederschlagen. Nach einem anderen Verfahren werden geschmolzene Wachse in einer Matrix aufgenommen ("microsponge"), die als Mikropartikel zusätzlich mit filmbildenden Polymeren umhüllt sein können. Die mikroskopisch kleinen Kapseln lassen sich wie Pulver trocknen. Neben einkernigen Mikrokapseln sind auch mehrkernige Aggregate, auch Mikrosphären genannt, bekannt, die zwei oder mehr Kerne im kontinuierlichen Hüllmaterial verteilt enthalten. Ein- oder mehrkernige Mikrokapseln können zudem von einer zusätzlichen zweiten, dritten etc. Hülle umschlossen sein. Die Hülle kann aus natürlichen, halbsynthetischen oder synthetischen Materialien bestehen. Natürlich Hüllmaterialien sind beispielsweise Gummi Arabicum, Agar-Agar, Agarose, Maltodextrine, Alginsäure bzw. ihre Salze, z.B. Natrium- oder Calciumalginat, Fette und Fettsäuren, Cetylalkohol, Collagen, Chitosan, Lecithine, Gelatine, Albumin, Schellack, Polysaccaride, wie Stärke oder Dextran, Polypeptide, Proteinhydrolysate, Sucrose und Wachse. Halbsynthetische Hüllmaterialien sind unter anderem chemisch modifizierte Cellulosen, insbesondere Celluloseester und -ether, z.B. Celluloseacetat, Ethylcellulose, Hydroxypropylcellulose, Hydroxypropylmethylcellulose und Carboxymethylcellulose, sowie Stärkederivate, insbesondere Stärkeether und -ester. Synthetische Hüllmaterialien sind beispielsweise Polymere wie Polyacrylate, Polyamide, Polyvinylalkohol oder Polyvinylpyrrolidon.The term "microcapsule" describes spherical aggregates with a Understand diameters in the range of about 0.1 to about 5 mm, the at least one contain solid or liquid core, which is enclosed by at least one continuous shell is. More specifically, they are coated with film-forming polymers finely dispersed liquid or solid phases, in the production of which the polymers change after emulsification and coacervation or interfacial polymerization on the material to be encased knock down. Another process involves melting waxes in a matrix added ("microsponge"), which as microparticles additionally with film-forming polymers can be enveloped. The microscopic capsules can be dried like powder. In addition to mononuclear microcapsules, multinuclear aggregates, also called microspheres, known that contain two or more cores distributed in the continuous shell material. Monocore or multi-core microcapsules can also have an additional second, third etc. envelope be enclosed. The shell can be natural, semi-synthetic or synthetic Materials exist. Of course, wrapping materials are, for example, gum arabic, Agar-agar, agarose, maltodextrins, alginic acid or their salts, e.g. Sodium or calcium alginate, Fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithins, gelatin, albumin, Shellac, polysaccharides, such as starch or dextran, polypeptides, protein hydrolyzates, Sucrose and waxes. Semi-synthetic shell materials include chemically modified ones Celluloses, especially cellulose esters and ethers, e.g. Cellulose acetate, ethyl cellulose, Hydroxypropyl cellulose, hydroxypropyl methyl cellulose and carboxymethyl cellulose, as well Starch derivatives, especially starch ethers and esters. There are synthetic wrapping materials for example polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinyl pyrrolidone.
Beispiele für Mikrokapseln des Stands der Technik sind folgende Handelsprodukte (in Klammern angegeben ist jeweils das Hüllmaterial) : Hallcrest Microcapsules (Gelatine, Gummi Arabicum), Coletica Thalaspheres (maritimes Collagen), Lipotec Millicapseln (Alginsäure, Agar-Agar), Induchem Unispheres (Lactose, mikrokristalline Cellulose, Hydroxypropylmethylcellulose); Unicerin C30 (Lactose, mikrokristalline Cellulose, Hydroxypropylmethylcellulose), Kobo Glycospheres (modifizierte Stärke, Fettsäureester, Phospholipide), Softspheres (modifiziertes Agar-Agar) und Kuhs Probiol Nanospheres (Phospholipide).Examples of microcapsules of the prior art are the following commercial products (in each case the shell material is given in brackets): Hallcrest microcapsules (gelatin, gum arabic), Coletica Thalaspheres (maritime collagen), Lipotec millicapsules (alginic acid, agar), induchem unispheres (lactose , microcrystalline cellulose, hydroxypropylmethyl cellulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified agar) and Kuhs Probiol Nanospheres (phospholipids).
In diesem Zusammenhang sei auch auf die deutsche Patentanmeldung DE 19712978 A1
(Henkel) hingewiesen, aus der Chitosanmikrosphären bekannt sind, die man erhält, indem
man Chitosane oder Chitosanderivate mit Ölkörpern vermischt und diese Mischungen in alkalisch
eingestellte Tensidlösungen einbringt. Aus der deutschen Patentanmeldung DE
19756452 A1 (Henkel) ist ferner auch die Verwendung von Chitosan als Verkapselungsmaterial
für Tocopherol bekannt. Chitosanmikrokapseln und Verfahren zu ihrer Herstellung
sind Gegenstand früherer Patenanmeldungen der Patentanmelderin [WO 01/01926, WO
01/01927, WO 01/01928, WO 01/01929]. Man unterscheidet dabei im wesentlichen
die beiden folgenden Verfahren:
Die Mikrokapseln des Stands der Technik sind jedoch nicht in jeder Hinsicht zufriedenstellend. Insbesondere erweisen sich die Kapseln als zu weich und insbesondere in der Hitze zu leicht verformbar, so dass der Wirkstoff zu rasch freigesetzt wird.However, the prior art microcapsules are not entirely satisfactory. In particular, the capsules turn out to be too soft and especially too hot easily deformable, so that the active ingredient is released too quickly.
Die Aufgabe der vorliegenden Erfindung hat somit darin bestanden, Mikrokapseln mit den bekannten vorteilhaften Eigenschaften zur Verfügung zu stellen, die jedoch über eine härtere Schale und verbesserte Resistenz gegenüber Wasser und Wärme verfügen.The object of the present invention was therefore to provide microcapsules with the to provide known advantageous properties, but which have a harder Shell and improved resistance to water and heat.
Gegenstand der Erfindung sind Vorgeschlagen neue Mikrokapseln mit mittleren Durchmessern
im Bereich von 0,1 bis 5 µm, bestehend aus einer doppelten Hüllmembran und einer
mindestens einen Wirkstoff enthaltenden Matrix, die dadurch erhältlich sind, dass man
Im ersten Schritt reagieren die anionischen Polymeren bzw. Polyacrylate mit dem Chitosan zu einer inneren Hüllmembran ab, die den Wirkstoff einschließt. Im zweiten Schritt reagiert dann nicht umgesetzte Aminogruppen des Chitosans mit den Polyacrylaten bzw. den anderen anionischen Polymeren unter Ausformung der äußeren Hülle, so dass ein Kapsel mit zwei hüllen entsteht. Diese neuen Mikrokapseln verfügen über verbesserte mechanische Eigenschaften. Sie werden weniger leicht von Wasser ausgewaschen, sind belastbarer und erweichen auch bei 40 °C nur langsam, was zusammengenommen in einer deutlich verzögerteren Freisetzung der verkapselten Wirkstoffe resultiert.In the first step, the anionic polymers or polyacrylates react with the chitosan to an inner envelope membrane that includes the active ingredient. The second step is to respond then unreacted amino groups of the chitosan with the polyacrylates or the others anionic polymers forming the outer shell, so that a capsule with two shells are created. These new microcapsules have improved mechanical ones Characteristics. They are less easily washed out by water, are more resilient and soften even slowly at 40 ° C, which together results in a significantly more delayed Release of the encapsulated active ingredients results.
Ein weiterer Gegenstand der Erfindung betrifft ein Verfahren zur Herstellung von Mikrokapseln
mit mittleren Durchmessern im Bereich von 0,1 bis 5 µm, bestehend aus einer doppelten
Hüllmembran und einer mindestens einen Wirkstoff enthaltenden Matrix, bei dem man
Die Auswahl der Wirkstoffe, die in den neuen Mikrokapseln eingeschlossen sind, ist an sich unkritisch. Vorzugsweise handelt es sich um Stoffe, die erst durch mechanische Zerstörung der Mikrokapseln freigesetzt werden. In diesen Fällen kommt den Mikrokapseln die Aufgabe zu, den Kontakt zwischen äußerer Umgebung und Wirkstoff und damit eine chemische Reaktion bzw. einen Abbau zu verhindern. Es kann es sein, dass die in der Kapsel eingeschlossenen Stoffe überhaupt nicht freigesetzt werden sollen und ausschließlich dem Zweck dienen, der Zubereitung ein ästhetisches Äußeres zu verleihen; dies trifft beispielsweise vielfach für Farbstoffe zu. Es ist natürlich klar, dass diese Einsatzformen auch nebeneinander bestehen können. Insbesondere ist es möglich, beispielsweise einen Duftstoff für die spätere Freisetzung zusammen mit einem Farbpigment zu verkapseln, welches der Kapsel ein besonderes Aussehen verleiht. The choice of active ingredients that are included in the new microcapsules is in itself critical. They are preferably substances that only result from mechanical destruction the microcapsules are released. In these cases, the microcapsules do the job to, the contact between the external environment and the active ingredient and thus a chemical reaction or to prevent degradation. It may be that those enclosed in the capsule Substances should not be released at all and only serve the purpose to give the preparation an aesthetic appearance; this is often the case for dyes too. It is of course clear that these types of use also exist side by side can. In particular, it is possible, for example, a fragrance for later release to encapsulate together with a color pigment, which makes the capsule a special one Gives appearance.
Typische Beispiele für Wirkstoffe, wie sie im Bereich der kosmetischen und pharmazeutischen Zubereitungen eingesetzt werden sind Tenside, kosmetische Öle, Perlglanzwachse, Stabilisatoren, biogene Wirkstoffe, Vitamine, Deodorantien, Antitranspirantien, Antischuppenmittel, UV-Lichtschutzfaktoren, Antioxidantien, Konservierungsmittel, Insektenrepellentien, Selbstbräuner, Typrosininhibitoren (Depigmentierungsmittel), Parfümöle, Aromen und Farbstoffe.Typical examples of active ingredients such as those in the cosmetic and pharmaceutical field Preparations are used are surfactants, cosmetic oils, pearlescent waxes, Stabilizers, biogenic agents, vitamins, deodorants, antiperspirants, antidandruff agents, UV light protection factors, antioxidants, preservatives, insect repellents, Self - tanners, typrosin inhibitors (depigmenting agents), perfume oils, flavors and Dyes.
Als oberflächenaktive Stoffe können anionische, nichtionische, kationische und/oder amphotere bzw. amphotere Tenside enthalten sein, deren Anteil an den Mitteln üblicherweise bei etwa 1 bis 70, vorzugsweise 5 bis 50 und insbesondere 10 bis 30 Gew.-% beträgt. Typische Beispiele für anionische Tenside sind Seifen, Alkylbenzolsulfonate, Alkansulfonate, Olefinsulfonate, Alkylethersulfonate, Glycerinethersulfonate, α-Methylestersulfonate, Sulfofettsäuren, Alkylsulfate, Fettalkoholethersulfate, Glycerinethersulfate, Fettsäureethersulfate, Hydroxymischethersulfate, Monoglycerid- (ether)sulfate, Fettsäureamid(ether)sulfate, Mono- und Dialkylsulfosuccinate, Monound Dialkylsulfosuccinamate, Sulfotriglyceride, Amidseifen, Ethercarbonsäuren und deren Salze, Fettsäureisethionate, Fettsäuresarcosinate, Fettsäuretauride, N-Acylaminosäuren, wie beispielsweise Acyllactylate, Acyltartrate, Acylglutamate und Acylaspartate, Alkyloligoglucosidsulfate, Proteinfettsäurekondensate (insbesondere pflanzliche Produkte auf Weizenbasis) und Alkyl(ether)phosphate. Sofern die anionischen Tenside Polyglycol-etherketten enthalten, können diese eine konventionelle, vorzugsweise jedoch eine eingeengte Homologenverteilung aufweisen. Typische Beispiele für nichtionische Tenside sind Fettalkoholpolyglycolether, Alkylphenolpolyglycolether, Fettsäurepolyglycolester, Fettsäureamidpolyglycolether, Fettaminpolyglycolether, alkoxylierte Triglyceride, Mischether bzw. Mischformale, gegebenenfalls partiell oxidierte Alk(en)yloligoglykoside bzw. Glucoronsäurederivate, Fettsäure-N-alkylglucamide, Proteinhydrolysate (insbesondere pflanzliche Produkte auf Weizenbasis), Polyolfettsäureester, Zuckerester, Sorbitanester, Polysorbate und Aminoxide. Sofern die nichtionischen Tenside Polyglycoletherketten enthalten, können diese eine konventionelle, vorzugsweise jedoch eine eingeengte Homologenverteilung aufweisen. Typische Beispiele für kationische Tenside sind quartäre Ammoniumverbindungen, wie beispielsweise das Dimethyldistearylammoniumchlorid, und Esterquats, insbesondere quaternierte Fettsäuretrialkanolaminestersalze. Typische Beispiele für amphotere bzw. zwitterionische Tenside sind Alkylbetaine, Alkylamidobetaine, Aminopropionate, Aminoglycinate, Imidazoliniumbetaine und Sulfobetaine. Bei den genannten Tensiden handelt es sich ausschließlich um bekannte Verbindungen. Hinsichtlich Struktur und Herstellung dieser Stoffe sei auf einschlägige Übersichtsarbeiten beispielsweise J.Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag, Berlin, 1987, S. 54-124 oder J.Falbe (ed.), "Katalysatoren, Tenside und Mineralöladditive", Thieme Verlag, Stuttgart, 1978, S. 123-217 verwiesen. Typische Beispiele für besonders geeignete milde, d.h. besonders hautverträgliche Tenside sind Fettalkoholpolyglycolethersulfate, Monoglyceridsulfate, Mono- und/oder Dialkylsulfosuccinate, Fettsäureisethionate, Fettsäuresarcosinate, Fettsäuretauride, Fettsäureglutamate, α-Olefinsulfonate, Ethercarbonsäuren, Alkyloligoglucoside, Fettsäureglucamide, Alkylamidobetaine, Amphoacetale und/oder Proteinfettsäurekondensate, letztere vorzugsweise auf Basis von Weizenproteinen.Anionic, nonionic, cationic and / or amphoteric or amphoteric surfactants may be present as surface-active substances, the proportion of which in the compositions is usually about 1 to 70, preferably 5 to 50 and in particular 10 to 30% by weight. Typical examples of anionic surfactants are soaps, alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, mono-ether ether sulfate, (hydroxymethoglysulfate), monohydric ether sulfate dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and salts thereof, fatty acid taurides, N-acylamino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (in particular vegetable products based on wheat) and alkyl (ether) phosphates , If the anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, optionally partially oxidized alk (en) yl oligoglycosides or especially glucoramide-acid-based vegetable derivatives, , Polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Typical examples of cationic surfactants are quaternary ammonium compounds, such as, for example, dimethyldistearylammonium chloride, and esterquats, in particular quaternized fatty acid trialkanolamine ester salts. Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The surfactants mentioned are exclusively known compounds. With regard to the structure and manufacture of these substances, reference is made to relevant reviews, for example, J.Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag, Berlin, 1987, pp. 54-124 or J.Falbe (ed.), "Catalysts, Tenside und Mineralöladditive ", Thieme Verlag, Stuttgart, 1978, pp. 123-217 . Typical examples of particularly suitable mild, ie particularly skin-compatible, surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid taurides, fatty acid glutamates, α-olefin sulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines, amphoacetals and / or protein fatty acid condensates, preferably based on wheat proteins.
Als kosmetische Öle kommen beispielsweise Guerbetalkohole auf Basis von Fettalkoholen mit 6 bis 18, vorzugsweise 8 bis 10 Kohlenstoffatomen, Ester von linearen C6-C22-Fettsäuren mit linearen C6-C22-Fettalkoholen, Ester von verzweigten C6-C13-Carbonsäuren mit linearen C6-C22-Fettalkoholen, wie z.B. Myristylmyristat, Myristylpalmitat, Myristylstearat, Myristylisostearat, Myristyloleat, Myristylbehenat, Myristylerucat, Cetylmyristat, Cetylpalmitat, Cetylstearat, Cetylisostearat, Cetyloleat, Cetylbehenat, Cetylerucat, Stearylmyristat, Stearylpalmitat, Stearylstearat, Stearylisostearat, Stearyloleat, Stearylbehenat, Stearylerucat, Isostearylmyristat, Isostearylpalmitat, Isostearylstearat, Isostearylisostearat, Isostearyloleat, Isostearylbehenat, Isostearyloleat, Oleylmyristat, Oleylpalmitat, Oleylstearat, Oleylisostearat, Oleyloleat, Oleylbehenat, Oleylerucat, Behenylmyristat, Behenylpalmitat, Behenylstearat, Behenylisostearat, Behenyloleat, Behenylbehenat, Behenylerucat, Erucylmyristat, Erucylpalmitat, Erucylstearat, Erucylisostearat, Erucyloleat, Erucylbehenat und Erucylerucat. Daneben eignen sich Ester von linearen C6-C22-Fettsäuren mit verzweigten Alkoholen, insbesondere 2-Ethylhexanol, Ester von Hydroxycarbonsäuren mit linearen oder verzweigten C6-C22-Fettalkoholen, insbesondere Dioctyl Malate, Ester von linearen und/oder verzweigten Fettsäuren mit mehrwertigen Alkoholen (wie z.B. Propylenglycol, Dimerdiol oder Trimertriol) und/oder Guerbetalkoholen, Triglyceride auf Basis C6-C10-Fettsäuren, flüssige Mono-/Di-/Trlglyceridmischungen auf Basis von C6-C18-Fettsäuren, Ester von C6-C22-Fettalkoholen und/oder Guerbetalkoholen mit aromatischen Carbonsäuren, insbesondere Benzoesäure, Ester von C2-C12-Dicarbonsäuren mit linearen oder verzweigten Alkoholen mit 1 bis 22 Kohlenstoffatomen oder Polyolen mit 2 bis 10 Kohlenstoffatomen und 2 bis 6 Hydroxylgruppen, pflanzliche Öle, verzweigte primäre Alkohole, substituierte Cyclohexane, lineare und verzweigte C6-C22-Fettalkoholcarbonate, Guerbetcarbonate, Ester der Benzoesäure mit linearen und/oder verzweigten C6-C22-Alkoholen (z.B. Finsolv® TN), lineare oder verzweigte, symmetrische oder unsymmetrische Dialkylether mit 6 bis 22 Kohlenstoffatomen pro Alkylgruppe, Ringöffnungsprodukte von epoxidierten Fettsäureestern mit Polyolen, Siliconöle und/oder aliphatische bzw. naphthenische Kohlenwasserstoffe, wie z.B. wie Squalan, Squalen oder Dialkylcyclohexane in Betracht.Cosmetic oils include, for example, Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C 6 -C 22 fatty acids with linear C 6 -C 22 fatty alcohols, esters of branched C 6 -C 13 - carboxylic acids with linear C 6 -C 22 -fatty alcohols, such as myristyl myristate, myristyl palmitate, myristyl stearate, Myristylisostearat, myristyl, Myristylbehenat, Myristylerucat, cetyl myristate, cetyl palmitate, cetyl stearate, Cetylisostearat, cetyl oleate, cetyl behenate, Cetylerucat, Stearylmyristat, stearyl palmitate, stearyl stearate, Stearylisostearat, stearyl oleate , stearyl, Stearylerucat, isostearyl, isostearyl, Isostearylstearat, isostearyl isostearate, Isostearyloleat, isostearyl behenate, Isostearyloleat, oleyl, oleyl palmitate, oleyl stearate, oleyl isostearate, oleate, Oleylbehenat, oleyl, behenyl myristate, behenyl, behenyl, Behenylisostearat, behenyl oleate, behenyl, erucyl, e rucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucylerucate. In addition, esters of linear C 6 -C 22 fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C 6 -C 22 fatty alcohols, in particular dioctyl malates, esters of linear and / or branched fatty acids are also suitable polyhydric alcohols (such as propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, triglycerides based on C 6 -C 10 fatty acids, liquid mono- / di- / trl glyceride mixtures based on C 6 -C 18 fatty acids, esters of C 6 -C 22 fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, especially benzoic acid, esters of C 2 -C 12 dicarboxylic acids with linear or branched alcohols with 1 to 22 carbon atoms or polyols with 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils , branched primary alcohols, substituted cyclohexanes, linear and branched C 6 -C 22 fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with lin earen and / or branched C 6 -C 22 alcohols (e.g. Finsolv® TN), linear or branched, symmetrical or unsymmetrical dialkyl ethers with 6 to 22 carbon atoms per alkyl group, ring opening products of epoxidized fatty acid esters with polyols, silicone oils and / or aliphatic or naphthenic Hydrocarbons, such as, for example, squalane, squalene or dialkylcyclohexanes.
Als Perlglanzwachse kommen beispielsweise in Frage: Alkylenglycolester, speziell Ethylenglycoldistearat; Fettsäurealkanolamide, speziell Kokosfettsäurediethanolamid; Partialglyceride, speziell Stearinsäuremonoglycerid; Ester von mehrwertigen, gegebenenfalls hydroxysubstituierte Carbonsäuren mit Fettalkoholen mit 6 bis 22 Kohlenstoffatomen, speziell langkettige Ester der Weinsäure; Fettstoffe, wie beispielsweise Fettalkohole, Fettketone, Fettaldehyde, Fettether und Fettcarbonate, die in Summe mindestens 24 Kohlenstoffatome aufweisen, speziell Lauron und Distearylether; Fettsäuren wie Stearinsäure, Hydroxystearinsäure oder Behensäure, Ringöffnungsprodukte von Olefinepoxiden mit 12 bis 22 Kohlenstoffatomen mit Fettalkoholen mit 12 bis 22 Kohlenstoffatomen und/oder Polyolen mit 2 bis 15 Kohlenstoffatomen und 2 bis 10 Hydroxylgruppen sowie deren Mischungen.Pearlescent waxes that can be used are, for example: alkylene glycol esters, especially ethylene glycol distearate; Fatty acid alkanolamides, especially coconut fatty acid diethanolamide; partial glycerides, especially stearic acid monoglyceride; Esters of polyvalent, if necessary hydroxy substituted carboxylic acids with fatty alcohols with 6 to 22 carbon atoms, especially long chain esters of tartaric acid; Fatty substances, such as fatty alcohols, Fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, totaling at least 24 Have carbon atoms, especially lauron and distearyl ether; Fatty acids such as stearic acid, Hydroxystearic acid or behenic acid, ring opening products of olefin epoxides with 12 to 22 carbon atoms with fatty alcohols with 12 to 22 carbon atoms and / or polyols with 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and their mixtures.
Als Stabilisatoren können Metallsalze von Fettsäuren, wie z.B. Magnesium-, Aluminiumund/Oder Zinkstearat bzw. -ricinoleat eingesetzt werden.Metal salts of fatty acids, such as e.g. Magnesium, aluminum and / or Zinc stearate or ricinoleate can be used.
Unter biogenen Wirkstoffen sind beispielsweise Tocopherol, Tocopherolacetat, Tocopherolpalmitat, Ascorbinsäure, Desoxyribonucleinsäure, Retinol, Retinylpalmitat, Bisabolol, Allantoin, Phytantriol, Panthenol, Menthol, Teebaumöl, AHA-Säuren, Kojisäure, Aminosäuren, Ceramide, Pseudoceramide, essentielle Öle, Pflanzenextrakte und Vitaminkomplexe zu verstehen. Examples of biogenic active ingredients are tocopherol, tocopherol acetate, tocopherol palmitate, Ascorbic acid, deoxyribonucleic acid, retinol, retinyl palmitate, bisabolol, Allantoin, phytantriol, panthenol, menthol, tea tree oil, AHA acids, kojic acid, amino acids, Ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes to understand.
Kosmetische Deodorantien (Desodorantien) wirken Körpergerüchen entgegen, überdecken oder beseitigen sie. Körpergerüche entstehen durch die Einwirkung von Hautbakterien auf apokrinen Schweiß, wobei unangenehm riechende Abbauprodukte gebildet werden. Dementsprechend enthalten Deodorantien Wirkstoffe, die als keimhemmende Mittel, Enzyminhibitoren, Geruchsabsorber oder Geruchsüberdecker fungieren.Cosmetic deodorants (deodorants) counteract body odors, mask them or eliminate them. Body odors arise from the action of skin bacteria on apocrine sweat, forming unpleasant smelling breakdown products become. Accordingly, deodorants contain active ingredients that are considered germ-inhibiting Agents, enzyme inhibitors, odor absorbers or odor maskers act.
Als keimhemmende Mittel sind grundsätzlich alle gegen grampositive Bakterien wirksamen Stoffe geeignet, wie z. B. 4-Hydroxybenzoesäure und ihre Salze und Ester, N-(4-Chlorphenyl)-N'-(3,4 dichlorphenyl)harnstoff, 2,4,4'-Trichlor-2'-hydroxydiphenylether (Triclosan), 4-Chlor-3,5-dimethylphenol, 2,2'-Methylen-bis(6-brom-4-chlorphenol), 3-Methyl-4-(1-methylethyl)phenol, 2-Benzyl-4-chlorphenol, 3-(4-Chlorphenoxy)-1,2-propandiol, 3-Iod-2-propinylbutylcarbamat, Chlorhexidin, 3,4,4'-Trichlorcarbanilid (TTC), antibakterielle Riechstoffe, Thymol, Thymianöl, Eugenol, Nelkenöl, Menthol, Minzöl, Farnesol, Phenoxyethanol, Glycerinmonolaurat (GML), Diglycerinmonocaprinat (DMC), Salicylsäure-N-alkylamide wie z. B. Salicylsäure-n-octylamid oder Salicylsäure-ndecylamid.All germs are effective as anti-germ agents against gram-positive bacteria Suitable fabrics such. B. 4-hydroxybenzoic acid and its salts and esters, N- (4-chlorophenyl) -N '- (3.4 dichlorophenyl) urea, 2,4,4'-trichloro-2'-hydroxydiphenyl ether (Triclosan), 4-chloro-3,5-dimethylphenol, 2,2'-methylene-bis (6-bromo-4-chlorophenol), 3-methyl-4- (1-methylethyl) phenol, 2-benzyl-4-chlorophenol, 3- (4-chlorophenoxy) -1,2-propanediol, 3-iodo-2-propynyl butyl carbamate, chlorhexidine, 3,4,4'-trichlorocarbanilide (TTC), antibacterial fragrances, thymol, thyme oil, eugenol, clove oil, menthol, mint oil, Farnesol, phenoxyethanol, glycerol monolaurate (GML), diglycerol monocaprinate (DMC), salicylic acid N-alkylamides such as e.g. B. salicylic acid n-octylamide or salicylic acid ndecylamide.
Als Enzyminhibitoren sind beispielsweise Esteraseinhibitoren geeignet. Hierbei handelt es sich vorzugsweise um Trialkylcitrate wie Trimethylcitrat, Tripropylcitrat, Triisopropylcitrat, Tributylcitrat und insbesondere Triethylcitrat (Hydagen® CAT, Henkel KGaA, Düsseldorf/FRG). Die Stoffe inhibieren die Enzymaktivität und reduzieren dadurch die Geruchsbildung. Weitere Stoffe, die als Esteraseinhibitoren in Betracht kommen, sind Sterolsulfate oder -phosphate, wie beispielsweise Lanosterin-, Cholesterin-, Campesterin-, Stigmasterin- und Sitosterinsulfat bzw -phosphat, Dicarbonsäuren und deren Ester, wie beispielsweise Glutarsäure, Glutarsäuremonoethylester, Glutarsäurediethylester, Adipinsäure, Adipinsäuremonoethylester, Adipinsäurediethylester, Malonsäure und Malonsäurediethylester, Hydroxycarbnonsäuren und deren Ester wie beispielsweise Citronensäure, Äpfelsäure, Weinsäure oder Weinsäurediethylester, sowie Zinkglycinat.Esterase inhibitors, for example, are suitable as enzyme inhibitors. This is about it is preferably trialkyl citrates such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, Tributyl citrate and especially triethyl citrate (Hydagen® CAT, Henkel KGaA, Düsseldorf / FRG). The substances inhibit enzyme activity and thereby reduce odor. Other substances that can be considered as esterase inhibitors are sterolsulfates or phosphates, such as lanosterol, cholesterol, campesterol, Stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and their esters, such as for example glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, Monoethyl adipate, diethyl adipate, malonic acid and diethyl malonate, Hydroxycarboxylic acids and their esters such as citric acid, Malic acid, tartaric acid or tartaric acid diethyl ester, as well as zinc glycinate.
Als Geruchsabsorber eignen sich Stoffe, die geruchsbildende Verbindungen aufnehmen und weitgehend festhalten können. Sie senken den Partialdruck der einzelnen Komponenten und verringern so auch ihre Ausbreitungsgeschwindigkeit. Wichtig ist, daß dabei Parfums unbeeinträchtigt bleiben müssen. Geruchsabsorber haben keine Wirksamkeit gegen Bakterien. Sie enthalten beispielsweise als Hauptbestandteil ein komplexes Zinksalz der Ricinolsäure oder spezielle, weitgehend geruchsneutrale Duftstoffe, die dem Fachmann als "Fixateure" bekannt sind, wie z. B. Extrakte von Labdanum bzw. Styrax oder bestimmte Abietinsäurederivate. Als Geruchsüberdecker fungieren Riechstoffe oder Parfümöle, die zusätzlich zu ihrer Funktion als Geruchsüberdecker den Deodorantien ihre jeweilige Duftnote verleihen. Als Parfümöle seien beispielsweise genannt Gemische aus natürlichen und synthetischen Riechstoffen. Natürliche Riechstoffe sind Extrakte von Blüten, Stengeln und Blättern, Früchten, Fruchtschalen, Wurzeln, Hölzern, Kräutern und Gräsern, Nadeln und Zweigen sowie Harzen und Balsamen. Weiterhin kommen tierische Rohstoffe in Frage, wie beispielsweise Zibet und Castoreum. Typische synthetische Riechstoffverbindungen sind Produkte vom Typ der Ester, Ether, Aldehyde, Ketone, Alkohole und Kohlenwasserstoffe. Riechstoffverbindungen vom Typ der Ester sind z.B. Benzylacetat, p-tert.-Butylcyclohexylacetat, Linalylacetat, Phenylethylacetat, Linalylbenzoat, Benzylformiat, Allylcyclohexylpropionat, Styrallylpropionat und Benzylsalicylat. Zu den Ethern zählen beispielsweise Benzylethylether, zu den Aldehyden z.B. die linearen Alkanale mit 8 bis 18 Kohlenstoffatomen, Citral, Citronellal, Citronellyloxyacetaldehyd, Cyclamenaldehyd, Hydroxycitronellal, Lilial und Bourgeonal, zu den Ketonen z.B. die Jonone und Methylcedrylketon, zu den Alkoholen Anethol, Citronellol, Eugenol, Isoeugenol, Geraniol, Linalool, Phenylethylalkohol und Terpineol, zu den Kohlenwasserstoffen gehören hauptsächlich die Terpene und Balsame. Bevorzugt werden jedoch Mischungen verschiedener Riechstoffe verwendet, die gemeinsam eine ansprechende Duftnote erzeugen. Auch ätherische Öle geringerer Flüchtigkeit, die meist als Aromakomponenten verwendet werden, eignen sich als Parfümöle, z.B. Salbeiöl, Kamillenöl, Nelkenöl, Melissenöl, Minzenöl, Zimtblätteröl, Lindenblütenöl, Wacholderbeerenöl, Vetiveröl, Olibanöl, Galbanumöl, Labdanumöl und Lavandinöl. Vorzugsweise werden Bergamotteöl, Dihydromyrcenol, Lilial, Lyral, Citronellol, Phenylethylalkohol, α-Hexylzimtaldehyd, Geraniol, Benzylaceton, Cyclamenaldehyd, Linalool, Boisambrene Forte, Ambroxan, Indol, Hedione, Sandelice, Citronenöl, Mandarinenöl, Orangenöl, Allylamylglycolat, Cyclovertal, Lavandinöl, Muskateller Salbeiöl, β-Damascone, Geraniumöl Bourbon, Cyclohexylsalicylat, Vertofix Coeur, Iso-E-Super, Fixolide NP, Evernyl, Iraldein gamma, Phenylessigsäure, Geranylacetat, Benzylacetat, Rosenoxid, Romilat, Irotyl und Floramat allein oder in Mischungen, eingesetzt.Substances which absorb odor-forming compounds are suitable as odor absorbers and can hold on to a large extent. They reduce the partial pressure of the individual components and thus reduce their speed of propagation. It is important that Perfumes must remain unaffected. Odor absorbers have no effectiveness against bacteria. For example, they contain a complex zinc salt as the main component the ricinoleic acid or special, largely odorless fragrances that the Are known in the art as "fixators" such. B. extracts of Labdanum or Styrax or certain abietic acid derivatives. Fragrances or act as odor maskers Perfume oils that, in addition to their function as odor maskers, deodorants their give each fragrance note. Mixtures may be mentioned as perfume oils from natural and synthetic fragrances. Natural fragrances are extracts of flowers, stems and leaves, fruits, fruit peels, roots, woods, herbs and grasses, needles and twigs as well as resins and balms. Furthermore come animal Raw materials in question, such as civet and castoreum. Typical synthetic Fragrance compounds are products of the ester, ether, aldehyde, ketone, Alcohols and hydrocarbons. Fragrance compounds of the ester type are e.g. Benzyl acetate, p-tert-butylcyclohexyl acetate, linalyl acetate, phenylethyl acetate, linalyl benzoate, Benzyl formate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. To the ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear Alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g. the Jonone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, isoeugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons belong mainly to the terpenes and balms. However, mixtures are preferred different fragrances are used, which together produce an appealing fragrance. Also essential oils of lower volatility, mostly as aroma components are used as perfume oils, e.g. Sage oil, chamomile oil, clove oil, lemon balm oil, Mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, Galbanum oil, Labdanum oil and Lavandin oil. Bergamot oil, dihydromyrcenol, Lilial, Lyral, Citronellol, Phenylethyl alcohol, α-Hexylzimtaldehyd, Geraniol, Benzylacetone, cyclamenaldehyde, linalool, boisambrene forte, ambroxan, indole, hedione, Sandelice, lemon oil, mandarin oil, orange oil, allylamyl glycolate, cyclover valley, Lavandin oil, muscatel sage oil, β-damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, Evernyl, Iraldein gamma, phenylacetic acid, Geranyl acetate, benzyl acetate, rose oxide, romilat, irotyl and floramat alone or used in mixtures.
Antitranspirantien (Antiperspirantien) reduzieren durch Beeinflussung der Aktivität der ekkrinen Schweißdrüsen die Schweißbildung, und wirken somit Achselnässe und Körpergeruch entgegen. Als adstringierende Antitranspirant-Wirkstoffe eignen sich vor allem Salze des Aluminiums, Zirkoniums oder des Zinks. Solche geeigneten antihydrotisch wirksamen Wirkstoffe sind z.B. Aluminiumchlorid, Aluminiumchlorhydrat, Aluminiumdichlorhydrat, Aluminiumsesquichlorhydrat und deren Komplexverbindungen z. B. mit Propylenglycol-1,2. Aluminiumhydroxyallantoinat, Aluminiumchloridtartrat, Aluminium-Zirkonium-Trichlorohydrat, Aluminium-Zirkonium-tetrachlorohydrat, Aluminium-Zirkonium-pentachlorohydrat und deren Komplexverbindungen z. B. mit Aminosäuren wie Glycin. Daneben können in Antitranspirantien übliche öllösliche und wasserlösliche Hilfsmittel in geringeren Mengen enthalten sein. Solche öllöslichen Hilfsmittel können z.B.entzündungshemmende, hautschützende oder wohlriechende ätherische Öle, synthetische hautschützende Wirkstoffe und/oder öllösliche Parfümöle sein.Antiperspirants (antiperspirants) reduce by affecting the activity of the eccrine sweat glands sweat, and thus act armpit wetness and body odor opposite. Suitable as astringent antiperspirant active ingredients are above all Salts of aluminum, zirconium or zinc. Such suitable antiperspirant active ingredients are e.g. Aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, Aluminum sesquichlorohydrate and their complex compounds e.g. B. with 1,2-propylene glycol. Aluminum hydroxyallantoinate, aluminum chloride tartrate, aluminum zirconium trichlorohydrate, Aluminum zirconium tetrachlorohydrate, aluminum zirconium pentachlorohydrate and their complex compounds z. B. with amino acids like glycine. In addition, oil-soluble and water-soluble oils commonly used in antiperspirants Aids may be included in smaller quantities. Such oil-soluble aids can e.g. anti-inflammatory, skin-protecting or fragrant essential oils, synthetic skin-protecting agents and / or oil-soluble perfume oils.
Als Antischuppenmittel können Climbazol, Octopirox, Ketokonazol und Zinkpyrethion eingesetzt werden.Climbazole, octopirox, ketoconazole and zinc pyrethione can be used as antidandruff agents be used.
Unter UV-Lichtschutzfaktoren sind beispielsweise bei Raumtemperatur flüssig oder kristallin vorliegende organische Substanzen (Lichtschutzfilter) zu verstehen, die in der Lage sind, ultraviolette Strahlen zu absorbieren und die aufgenommene Energie in Form längerwelliger Strahlung, z.B. Wärme wieder abzugeben. UVB-Filter können öllöslich oder wasserlöslich sein. Als öllösliche Substanzen sind z.B. zu nennen : 3-Benzylidencampher bzw. 3-Benzylidennorcampher und dessen Derivate, z.B. 3-(4-Methylbenzyliden)campher wie in der EP 0693471 B1 beschrieben; 4-Aminobenzoesäurederivate, vorzugsweise 4-(Dimethylamino)benzoesäure-2-ethylhexyl-ester, 4-Dimethylamino)-benzoesäure-2-octylester und 4-(Dimethylamino)benzoesäure-amylester; Ester der Zimtsäure, vorzugsweise 4-Methoxyzimtsäure-2-ethylhexylester, 4-Methoxyzimtsäurepropyl-ester, 4-Methoxyzimtsäureisoamylester 2-Cyano-3,3-phenylzimtsäure-2-ethylhexylester (Octocrylene); Ester der Salicylsäure, vorzugsweise Salicylsäure-2-ethylhexylester, Salicylsäure-4-isopropylbenzylester, Salicylsäurehomomenthylester; Derivate des Benzophenons, vorzugsweise 2-Hydroxy-4-methoxybenzophenon, 2-Hydroxy-4-methoxy-4'-methylbenzophenon, 2,2'-Dihydroxy-4-methoxybenzophenon; Ester der Benzalmalonsäure, vorzugsweise 4-Methoxybenzmalonsäuredi-2-ethyl-hexylester; Triazinderivate, wie z.B. 2,4,6-Trianilino-(p-carbo-2'-ethyl-1'-hexyloxy)-1,3,5-triazin und Octyl Triazon, wie in der EP 0818450 A1 beschrieben oder Dioctyl Butamido Triazone (Uvasorb® HEB); Propan-1,3-dione, wie z.B. 1-(4-tert.Butylphenyl)-3-(4'methoxyphenyl)propan-1,3-dion; Ketotricyclo(5.2.1.0)decan-Derivate, wie in der EP 0694521 B1 beschrieben.UV light protection factors are, for example, liquid or crystalline at room temperature present organic substances (light protection filters) that are able to understand are to absorb ultraviolet rays and the absorbed energy in the form longer-wave radiation, e.g. To give off heat again. UVB filters can be oil-soluble or be water soluble. As oil-soluble substances e.g. to name: 3-benzylidene camphor or 3-benzylidene norcampher and its derivatives, e.g. 3- (4-methylbenzylidene) camphor as described in EP 0693471 B1; 4-aminobenzoic acid derivatives, preferably 2-octyl 4- (dimethylamino) benzoate, 2-octyl 4-dimethylamino) benzoate and 4- (dimethylamino) benzoic acid amyl ester; Esters of Cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, Isoamyl 4-methoxycinnamate 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (Octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylic acid, Salicylic acid 4-isopropyl benzyl ester, salicylic acid homomethyl ester; derivatives benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; ester benzalmalonic acid, preferably 4-methoxybenzmalonic acid di-2-ethylhexyl ester; Triazine derivatives, e.g. 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and Octyl triazone, as described in EP 0818450 A1 or dioctyl butamido triazone (Uvasorb® HEB); Propane-1,3-diones, e.g. 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives, as in the EP 0694521 B1.
Als wasserlösliche Substanzen kommen in Frage: 2-Phenylbenzimidazol-5-sulfonsäure und deren Alkali-, Erdalkali-, Ammonium-, Alkylammonium-, Alkanolammonium- und Glucammoniumsalze; Sulfonsäurederivate von Benzophenonen, vorzugsweise 2-Hydroxy-4-methoxybenzophenon-5-sulfonsäure und ihre Salze; Sulfonsäurederivate des 3-Benzylidencamphers, wie z.B. 4-(2-Oxo-3-bornylidenmethyl)benzolsulfonsäure und 2-Methyl-5-(2-oxo-3-bornyliden)sulfonsäure und deren Salze. Als typische UV-A-Filter kommen insbesondere Derivate des Benzoylmethans in Frage, wie beispielsweise 1-(4'tert.Butyl-phenyl)-3-(4'-methoxyphenyl)propan-1,3-dion, 4-tert.-Butyl-4'-methoxydibenzoyl-methan (Parsol 1789), 1-Phenyl-3-(4'-isopropylphenyl)-propan-1,3-dion sowie E-naminverbindungen, wie beschrieben in der DE 19712033 A1 (BASF). Die UV-A und UVB-Filter können selbstverständlich auch in Mischungen eingesetzt werden. Neben den genannten löslichen Stoffen kommen für diesen Zweck auch unlösliche Lichtschutzpigmente, nämlich feindisperse Metalloxide bzw. Salze in Frage. Beispiele für geeignete Metalloxide sind insbesondere Zinkoxid und Titandioxid und daneben Oxide des Eisens, Zirkoniums, Siliciums, Mangans, Aluminiums und Cers sowie deren Gemische. Als Salze können Silicate (Talk), Bariumsulfat oder Zinkstearat eingesetzt werden. Die Oxide und Salze werden in Form der Pigmente für hautpflegende und hautschützende Emulsionen und dekorative Kosmetik verwendet. Die Partikel sollten dabei einen mittleren Durchmesser von weniger als 100 nm, vorzugsweise zwischen 5 und 50 nm und insbesondere zwischen 15 und 30 nm aufweisen. Sie können eine sphärische Form aufweisen, es können jedoch auch solche Partikel zum Einsatz kommen, die eine ellipsoide oder in sonstiger Weise von der sphärischen Gestalt abweichende Form besitzen. Die Pigmente können auch oberflächenbehandelt, d.h. hydrophilisiert oder hydrophobiert vorliegen. Typische Beispiele sind gecoatete Titandioxide, wie z.B. Titandioxid T 805 (Degussa) oder Eusolex® T2000 (Merck). Als hydrophobe Coatingmittel kommen dabei vor allem Silicone und dabei speziell Trialkoxyoctylsilane oder Simethicone in Frage. In Sonnenschutzmitteln werden als verkapselte Wirkstoffe bevorzugt sogenannte Mikro- oder Nanopigmente eingesetzt. Vorzugsweise wird mikronisiertes Zinkoxid verwendet. Weitere geeignete UV-Lichtschutzfilter sind der Übersicht von P.Finkel in SÖFW-Journal 122, 543 (1996) zu entnehmen.Possible water-soluble substances are: 2-phenylbenzimidazole-5-sulfonic acid and their alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and their salts; Sulfonic acid derivatives of 3-benzylidene camphers, e.g. 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts. As a typical UV-A filter derivatives of benzoylmethane are particularly suitable, such as 1- (4'-tert-butyl-phenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl-4'-methoxydibenzoyl-methane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and also E-namin compounds, as described in DE 19712033 A1 (BASF). The UV-A and UVB filters can of course also be used in mixtures. In addition to the the soluble substances mentioned also come with insoluble light protection pigments for this purpose, namely finely dispersed metal oxides or salts in question. Examples of suitable ones Metal oxides are in particular zinc oxide and titanium dioxide and also oxides of iron, Zirconium, silicon, manganese, aluminum and cerium and their mixtures. As salts Silicates (talc), barium sulfate or zinc stearate can be used. The oxides and Salts are in the form of pigments for skin-care and skin-protecting emulsions and used decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular have between 15 and 30 nm. They can have a spherical shape, it However, particles can also be used that have an ellipsoidal or in otherwise have a shape deviating from the spherical shape. The pigments can also be surface treated, i.e. are hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, e.g. Titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). The main hydrophobic coating agents are Silicones and especially trialkoxyoctylsilanes or simethicones in question. In sunscreens so-called micro- or nanopigments are preferred as encapsulated active ingredients used. Micronized zinc oxide is preferably used. Further Suitable UV light protection filters are in the overview by P.Finkel in SÖFW-Journal 122, 543 (1996).
Neben den beiden vorgenannten Gruppen primärer Lichtschutzstoffe können auch sekundäre Lichtschutzmittel vom Typ der Antioxidantien eingesetzt werden, die die photochemische Reaktionskette unterbrechen, welche ausgelöst wird, wenn UV-Strahlung in die Haut eindringt. Typische Beispiele hierfür sind Aminosäuren (z.B. Glycin, Histidin, Tyrosin, Tryptophan) und deren Derivate, Imidazole (z.B. Urocaninsäure) und deren Derivate, Peptide wie D,L-Carnosin, D-Carnosin, L-Carnosin und deren Derivate (z.B. Anserin), Carotinoide, Carotine (z.B. α-Carotin, β-Carotin, Lycopin) und deren Derivate, Chlorogensäure und deren Derivate, Liponsäure und deren Derivate (z.B. Dihydroliponsäure), Aurothioglucose, Propylthiouracil und andere Thiole (z.B. Thioredoxin, Glutathion, Cystein, Cystin, Cystamin und deren Glycosyl-, N-Acetyl-, Methyl-, Ethyl-, Propyl-, Amyl- , Butyl- und Lauryl-, Palmitoyl-, Oleyl-, γ-Linoleyl-, Cholesteryl- und Glycerylester) sowie deren Salze, Dilaurylthiodipropionat, Distearylthiodipropionat, Thiodipropionsäure und deren Derivate (Ester, Ether, Peptide, Lipide, Nukleotide, Nukleoside und Salze) sowie Sulfoximinverbindungen (z.B. Buthioninsulfoximine, Homocysteinsulfoximin, Butioninsulfone, Penta-, Hexa-, Heptathioninsulfoximin) in sehr geringen verträglichen Dosierungen (z.B. pmol bis µmol/kg), ferner (Metall)-Chelatoren (z.B. α-Hydroxyfettsäuren, Palmitinsäure, Phytinsäure, Lactoferrin), α-Hydroxysäuren (z.B. Citronensäure, Milchsäure, Äpfelsäure), Huminsäure, Gallensäure, Gallenextrakte, Bilirubin, Biliverdin, EDTA, EGTA und deren Derivate, ungesättigte Fettsäuren und deren Derivate (z.B. γ-Linolensäure, Linolsäure, Ölsäure), Folsäure und deren Derivate, Ubichinon und Ubichinol und deren Derivate, Vitamin C und Derivate (z.B. Ascorbylpalmitat, Mg-Ascorbylphosphat, Ascorbylacetat), Tocopherole und Derivate (z.B. Vitamin-Eacetat), Vitamin A und Derivate (Vitamin-A-palmitat) sowie Koniferylbenzoat des Benzoeharzes, Rutinsäure und deren Derivate, α-Glycosylrutin, Ferulasäure, Furfurylidenglucitol, Carnosin, Butylhydroxytoluol, Butylhydroxyanisol, Nordihydroguajakharzsäure, Nordihydroguajaretsäure, Trihydroxybutyrophenon, Harnsäure und deren Derivate, Mannose und deren Derivate, Superoxid-Dismutase, Zink und dessen Derivate (z.B. ZnO, ZnSO4) Selen und dessen Derivate (z.B. Selen-Methionin), Stilbene und deren Derivate (z.B. Stilbenoxid, trans-Stilbenoxid) und die erfindungsgemäß geeigneten Derivate (Salze, Ester, Ether, Zucker, Nukleotide, Nukleoside, Peptide und Lipide) dieser genannten Wirkstoffe.In addition to the two aforementioned groups of primary light stabilizers, secondary light stabilizers of the antioxidant type can also be used, which interrupt the photochemical reaction chain which is triggered when UV radiation penetrates the skin. Typical examples are amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (e.g. anserine) , Carotenoids, carotenes (e.g. α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and their derivatives, lipoic acid and their derivatives (e.g. dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, Cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate , Distearylthiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (e.g. buthioninsulfoximines, homocysteine sulfoximine, butioninsulfones, penta-, hexa-, heptathioninsulfoximine) in very low ver inert dosages (e.g. pmol to µmol / kg), (metal) chelators (e.g. α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, Biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g. γ-linolenic acid, linoleic acid, oleic acid), folic acid and their derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (e.g. ascorbyl palmitate, Mg-ascorbyl phosphate, ascorbyl acetate ), Tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) as well as coniferyl benzoate of benzoin, rutinic acid and its derivatives, α-glycosyl rutin, ferulic acid, furfurylidene glucitol, carnosine, butylated hydroxytoluene, butylated hydroxyanic acid, nordihydrochloric acid, nordihydroidic acid, nordihydrochloric acid, nordihydrochloric acid, nordihydro acid acid , Trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, superoxide dismutase, zinc and its Derivatives (eg ZnO, ZnSO 4 ) selenium and its derivatives (eg selenium-methionine), stilbenes and their derivatives (eg stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these active ingredients.
Als Konservierungsmittel eignen sich beispielsweise Phenoxyethanol, Formaldehydlösung, Parabene, Pentandiol oder Sorbinsäure sowie die in Anlage 6, Teil A und B der Kosmetikverordnung aufgeführten weiteren Stoffklassen. Als Insekten-Repellentien kommen N,N-Diethyl-m-toluamid, 1,2-Pentandiol oder Ethyl Butylacetylaminopropionate in Frage, als Selbstbräuner eignet sich Dihydroxyaceton. Als Tyrosinhinbitoren, die die Bildung von Melanin verhindern und Anwendung in Depigmentie-rungsmitteln finden, kommen beispielsweise Arbutin, Kojisäure, Cumarinsäure und Ascorbinsäure (Vitamin C) in Frage. Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, Parabens, pentanediol or sorbic acid as well as those in Appendix 6, Parts A and B further cosmetic classes listed in the Cosmetics Ordinance. As insect repellents come N, N-diethyl-m-toluamide, 1,2-pentanediol or ethyl butylacetylaminopropionate in question, dihydroxyacetone is suitable as a self-tanner. As tyrosine inhibitors, the Prevent the formation of melanin and find application in depigmenting agents, arbutin, kojic acid, coumaric acid and ascorbic acid (vitamin C) in question.
Als Parfümöle seien genannt Gemische aus natürlichen und synthetischen Riechstoffen. Natürliche Riechstoffe sind Extrakte von Blüten (Lilie, Lavendel, Rosen, Jasmin, Neroli, Ylang-Ylang), Stengeln und Blättern (Geranium, Patchouli, Petitgrain), Früchten (Anis, Koriander, Kümmel, Wacholder), Fruchtschalen (Bergamotte, Zitrone, Orangen), Wurzeln (Macis, Angelica, Sellerie, Kardamon, Costus, Iris, Calmus), Hölzern (Pinien-, Sandel-, Guajak-, Zedern-, Rosenholz), Kräutern und Gräsern (Estragon, Lemongras, Salbei, Thymian), Nadeln und Zweigen (Fichte, Tanne, Kiefer, Latschen), Harzen und Balsamen (Galbanum, Elemi, Benzoe, Myrrhe, Olibanum, Opoponax). Weiterhin kommen tierische Rohstoffe in Frage, wie beispielsweise Zibet und Castoreum. Typische synthetische Riechstoffverbindungen sind Produkte vom Typ der Ester, Ether, Aldehyde, Ketone, Alkohole und Kohlenwasserstoffe. Riechstoffverbindungen vom Typ der Ester sind z.B. Benzylacetat, Phenoxyethylisobutyrat, p-tert.-Butylcyclohexylacetat, Linalylacetat, Dimethylbenzylcarbinylacetat, Phenylethylacetat, Linalylbenzoat, Benzylformiat, Ethylmethylphenylglycinat, Allylcyclohexylpropionat, Styrallylpropionat und Benzylsalicylat. Zu den Ethern zählen beispielsweise Benzylethylether, zu den Aldehyden z.B. die linearen Alkanale mit 8 bis 18 Kohlenstoffatomen, Citral, Citronellal, Citronellyloxyacetaldehyd, Cyclamenaldehyd, Hydroxycitronellal, Lilial und Bourgeonal, zu den Ketonen z.B. die Jonone, ∝-Isomethylionon und Methylcedrylketon, zu den Alkoholen Anethol, Citronellol, Eugenol, Isoeugenol, Geraniol, Linalool, Phenylethylalkohol und Terpineol, zu den Kohlenwasserstoffen gehören hauptsächlich die Terpene und Balsame. Bevorzugt werden jedoch Mischungen verschiedener Riechstoffe verwendet, die gemeinsam eine ansprechende Duftnote erzeugen. Auch ätherische Öle geringerer Flüchtigkeit, die meist als Aromakomponenten verwendet werden, eignen sich als Parfümöle, z.B. Salbeiöl, Kamillenöl, Nelkenöl, Melissenöl, Minzenöl, Zimtblätteröl, Lindenblütenöl, Wacholderbeerenöl, Vetiveröl, Olibanöl, Galbanumöl, Labolanumöl und Lavandinöl. Vorzugsweise werden Bergamotteöl, Dihydromyrcenol, Lilial, Lyral, Citronellol, Phenylethylalkohol, α-Hexylzimtaldehyd, Geraniol, Benzylaceton, Cyclamenaldehyd, Linalool, Boisambrene Forte, Ambroxan, Indol, Hedione, Sandelice, Citronenöl, Mandarinenöl, Orangenöl, Allylamylglycolat, Cyclovertal, Lavandinöl, Muskateller Salbeiöl, β-Damascone, Geraniumöl Bourbon, Cyclohexylsalicylat, Vertofix Coeur, Iso-E-Super, Fixolide NP, Evernyl, Iraldein gamma, Phenylessigsäure, Geranylacetat, Benzylacetat, Rosenoxid, Romilllat, Irotyl und Floramat allein oder in Mischungen, eingesetzt.Perfume oils include mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers (lily, lavender, roses, jasmine, neroli, Ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, Coriander, caraway, juniper), fruit peels (bergamot, lemon, oranges), roots (Macis, Angelica, Celery, Cardamom, Costus, Iris, Calmus), Woods (Pine, Sandal, Guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, Thyme), needles and twigs (spruce, fir, pine, mountain pine), resins and balsams (Galbanum, Elemi, Benzoe, Myrrh, Olibanum, Opoponax). Furthermore come animal Raw materials in question, such as civet and castoreum. Typical synthetic Fragrance compounds are products of the ester, ether, aldehyde, ketone, and alcohol type and hydrocarbons. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. To the ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear Alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g. the Jonone, ∝-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, Eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons belong mainly to the terpenes and balms. To be favoured however, mixtures of different fragrances are used, which together make an appealing Generate fragrance. Also essential oils of lower volatility, mostly as aroma components are used as perfume oils, e.g. Sage oil, chamomile oil, Clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, Vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil. Preferably be Bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexyl cinnamaldehyde, Geraniol, benzylacetone, cyclamenaldehyde, linalool, boisambrene Forte, Ambroxan, Indol, Hedione, Sandelice, lemon oil, mandarin oil, orange oil, allylamyl glycolate, Cyclover Valley, Lavandin Oil, Muscat Sage Oil, β-Damascone, Geranium Oil Bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, Evernyl, Iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilllate, irotyl and Floramat used alone or in mixtures.
Als Farbstoffe können die für kosmetische Zwecke geeigneten und zugelassenen Substanzen verwendet werden, wie sie beispielsweise in der Publikation "Kosmetische Färbemittel" der Farbstoffkommission der Deutschen Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, S.81-106 zusammengestellt sind. Diese Wirkstoffe können auch ausschließlich aus ästhetischen Gründen in den Kapseln enthalten und nicht für eine kontrollierte Freigabe vorgesehen sein.Suitable dyes are those which are suitable and approved for cosmetic purposes are used, such as those used in the publication "Cosmetic Colorants" the dye commission of the German Research Foundation, Verlag Chemie, Weinheim, 1984, p.81-106 are compiled. These agents can too Contained in the capsules only for aesthetic reasons and not for one controlled release.
Ein zweiter Einsatzbereich der neuen Mikrokapseln besteht in der Ausrüstung von Textilien. Der besondere Vorteil liegt hier darin, dass die Kapseln bei deutlich höheren Temperaturen erweichen und das Flammschutzmittel nicht zu früh freisetzen. Typische Beispiele für geeignete Wirkstoffe sind alle Arten von Flammschutzmitteln, also Metalloxide, wie z.B. Magnesiumoxid, Calciumoxid, Aluminiumoxid oder Antimon(III)oxid, organische Halide, wie z.B. Tetrabrombisphenol A oder Decabromodiphenyloxid sowie insbesondere organische Phosphorverbindungen, wie z.B. Triphenylphosphat (TPP), Tricresylphosphat (TCP), Cresyldiphenylphosphat (CDP) oder Tetraphenyldiphosphat. Die Mittel werden vorzugsweise mit Teilchengrößen im Bereich von 0,1 bis 5 mm eingesetzt.A second area of application for the new microcapsules is in the finishing of textiles. The particular advantage here is that the capsules at significantly higher temperatures soften and do not release the flame retardant too early. Typical examples of suitable ones Active substances are all types of flame retardants, i.e. metal oxides, e.g. magnesium oxide, Calcium oxide, aluminum oxide or antimony (III) oxide, organic halides, such as e.g. Tetrabromobisphenol A or decabromodiphenyl oxide and in particular organic phosphorus compounds, such as. Triphenyl phosphate (TPP), tricresyl phosphate (TCP), cresyl diphenyl phosphate (CDP) or tetraphenyl diphosphate. The agents are preferably with particle sizes used in the range of 0.1 to 5 mm.
In Summe werden die Wirkstoffe in solchen Mengen eingesetzt, dass ihr Anteil an den fertigen Mikrokapseln üblicherweise 1 bis 25, vorzugsweise 5 bis 15 und insbesondere 8 bis 10 Gew.-% beträgt.In total, the active ingredients are used in such quantities that their share in the finished ones Microcapsules usually 1 to 25, preferably 5 to 15 and in particular 8 to 10 % By weight.
Die Alginate und/oder Carboxymethylcellulosen haben die Aufgabe, mit den Chitosanen die inneren Membranen zu bilden. Für diesen Zweck eignen sich vorzugsweise Salze der Alginsäure. Bei der Alginsäure handelt es sich um ein Gemisch carboxylgruppenhaltiger Polysaccharide mit folgendem idealisierten Monomerbaustein: Das durchschnittliche Molekulargewicht der Alginsäuren bzw. der Alginate liegt im Bereich von 150.000 bis 250.000. Dabei sind als Salze der Alginsäure sowohl deren vollständige als auch deren partiellen Neutralisationsprodukte zu verstehen, insbesondere die Alkalisalze und hierunter vorzugsweise das Natriumalginat ("Algin") sowie die Ammonium- und Erdalkalisalze. besonders bevorzugt sind Mischalginate, wie z.B. Natrium/Magnesium- oder Natrium/Calciumalginate. In einer alternativen Ausführungsform der Erfindung kommen für diesen Zweck auch Carboxymethylcellulosen in Frage, insbesondere solche, die als übliche Waschmittelzusatzstoffe bereits im Handel erhältlich sind. In der Regel werden die Alginate und/oder Carboxymethylcellulosen in solchen Mengen eingesetzt, dass ihr Anteil an den fertigen Mikrokapseln 20 bis 40, vorzugsweise 25 bis 35 und insbesondere um die 30 Gew.-% beträgt.The alginates and / or carboxymethyl celluloses have the task of forming the inner membranes with the chitosans. Salts of alginic acid are preferably suitable for this purpose. Alginic acid is a mixture of carboxyl-containing polysaccharides with the following idealized monomer unit: The average molecular weight of the alginic acids or alginates is in the range from 150,000 to 250,000. Salts of alginic acid are to be understood as meaning both their complete and their partial neutralization products, in particular the alkali metal salts and among these preferably the sodium alginate (“algin”) and the ammonium and alkaline earth metal salts. Mixed alginates, such as sodium / magnesium or sodium / calcium alginates, are particularly preferred. In an alternative embodiment of the invention, carboxymethyl celluloses are also suitable for this purpose, in particular those which are already commercially available as customary detergent additives. As a rule, the alginates and / or carboxymethyl celluloses are used in amounts such that their proportion in the finished microcapsules is 20 to 40, preferably 25 to 35 and in particular around 30% by weight.
In einer bevorzugten Ausführungsform der vorliegenden Erfindung werden die Wirkstoffe
und Alginate bzw. Carboxymethylcellulosen gemeinsam mit Emulgatoren eingesetzt, um die
Bildung der O/W-Emulsionen zu unterstützen. Als Emulgatoren kommen beispielsweise
nichtionogene Tenside aus mindestens einer der folgenden Gruppen in Frage:
Die Anlagerungsprodukte von Ethylenoxid und/oder von Propylenoxid an Fettalkohole, Fettsäuren, Alkylphenole oder an Ricinusöl stellen bekannte, im Handel erhältliche Produkte dar. Es handelt sich dabei um Homologengemische, deren mittlerer Alkoxylierungsgrad dem Verhältnis der Stoffmengen von Ethylenoxid und/ oder Propylenoxid und Substrat, mit denen die Anlagerungsreaktion durchgeführt wird, entspricht. C12/18-Fettsäuremono- und -diester von Anlagerungsprodukten von Ethylenoxid an Glycerin sind aus DE 2024051 PS als Rückfettungsmittel für kosmetische Zubereitungen bekannt.The adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols or with castor oil are known, commercially available products. These are mixtures of homologs whose average degree of alkoxylation is the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate, with which the addition reaction is carried out. C 12/18 fatty acid monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE 2024051 PS as refatting agents for cosmetic preparations.
Alkyl- und/oder Alkenyloligoglycoside, ihre Herstellung und ihre Verwendung sind aus dem Stand der Technik bekannt. Ihre Herstellung erfolgt insbesondere durch Umsetzung von Glucose oder Oligosacchariden mit primären Alkoholen mit 8 bis 18 Kohlenstoffatomen. Bezüglich des Glycosidrestes gilt, daß sowohl Monoglycoside, bei denen ein cyclischer Zuckerrest glycosidisch an den Fettalkohol gebunden ist, als auch oligomere Glycoside mit einem Oligomerisationsgrad bis vorzugsweise etwa 8 geeignet sind. Der Oligomerisierungsgrad ist dabei ein statistischer Mittelwert, dem eine für solche technischen Produkte übliche Homologenverteilung zugrunde liegt. Alkyl and / or alkenyl oligoglycosides, their preparation and their use are out known in the art. They are manufactured in particular through implementation of glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms. Regarding the Glycosidrestes applies that both monoglycosides in which a cyclic sugar residue is glycosidically bound to the fatty alcohol, as well as oligomeric Glycosides with a degree of oligomerization of up to preferably about 8 are suitable. The Degree of oligomerization is a statistical mean, one for such technical Products based on the usual homolog distribution.
Typische Beispiele für geeignete Partialglyceride sind Hydroxystearinsäuremonoglycerid, Hydroxystearinsäurediglycerid, Isostearinsäuremonoglycerid, Isostearinsäurediglycerid, Ölsäuremonoglycerid, Ölsäurediglycerid, Ricinolsäuremoglycerid, Ricinolsäurediglycerid, Linolsäuremonoglycerid, Linolsäurediglycerid, Linolensäuremonoglycerid, Linolensäurediglycerid, Erucasäuremonoglycerid, Erucasäurediglycerid, Weinsäuremonoglycerid, Weinsäurediglycerid, Citronensäuremonoglycerid, Citronendiglycerid, Äpfelsäuremonoglycerid, Äpfelsäurediglycerid sowie deren technische Gemische, die untergeordnet aus dem Herstellungsprozeß noch geringe Mengen an Triglycerid enthalten können. Ebenfalls geeignet sind Anlagerungsprodukte von 1 bis 30, vorzugsweise 5 bis 10 Mol Ethylenoxid an die genannten Partialglyceride.Typical examples of suitable partial glycerides are hydroxystearic acid monoglyceride, Hydroxystearic acid diglyceride, isostearic acid monoglyceride, isostearic acid diglyceride, Oleic acid monoglyceride, oleic acid diglyceride, ricinoleic acid moglyceride, ricinoleic acid diglyceride, Linoleic acid monoglyceride, linoleic acid diglyceride, linolenic acid monoglyceride, linolenic acid diglyceride, Erucic acid monoglyceride, erucic acid diglyceride, tartaric acid monoglyceride, Tartaric acid diglyceride, citric acid monoglyceride, citric diglyceride, malic acid monoglyceride, Malic acid diglyceride and their technical mixtures, the subordinate may still contain small amounts of triglyceride from the manufacturing process. Likewise Addition products of 1 to 30, preferably 5 to 10, mol ethylene oxide are suitable to the partial glycerides mentioned.
Als Sorbitanester kommen Sorbitanmonoisostearat, Sorbitansesquiisostearat, Sorbitandiisostearat, Sorbitantriisostearat, Sorbitanmonooleat, Sorbitansesquioleat, Sorbitandioleat, Sorbitantrioleat, Sorbitanmonoerucat, Sorbitansesquierucat, Sorbitandierucat, Sorbitantrierucat, Sorbitanmonoricinoleat, Sorbitansesquiricinoleat, Sorbitandiricinoleat, Sorbitantriricinoleat, Sorbitanmonohydroxystearat, Sorbitansesquihydroxystearat, Sorbitandihydroxystearat, Sorbitantrihydroxystearat, Sorbitanmonotartrat, Sorbitansesquitartrat, Sorbitanditartrat, Sorbitantritartrat, Sorbitanmonocitrat, Sorbitansesquicitrat, Sorbitandicitrat, Sorbitantricitrat, Sorbitanmonomaleat, Sorbitansesquimaleat, Sorbitandimaleat, Sorbitantrimaleat sowie deren technische Gemische. Ebenfalls geeignet sind Anlagerungsprodukte von 1 bis 30, vorzugsweise 5 bis 10 Mol Ethylenoxid an die genannten Sorbitanester.Sorbitan monoisostearate, sorbitan sesquiisostearate, sorbitan diisostearate, Sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, Sorbitan trioleate, sorbitan monoerucate, sorbitan sesquierucate, sorbitan dierucate, Sorbitan trierucate, sorbitan monoricinoleate, sorbitan sesquicinoleate, sorbitan diricinoleate, Sorbitan triricinoleate, sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitan dihydroxy stearate, Sorbitan trihydroxystearate, sorbitan monotartrate, sorbitan sesquitartrate, Sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, Sorbitan citrate, sorbitan tricrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan maleate, Sorbitan trimaleate and their technical mixtures. Are also suitable Addition products of 1 to 30, preferably 5 to 10, moles of ethylene oxide to the above Sorbitan.
Typische Beispiele für geeignete Polyglycerinester sind Polyglyceryl-2 Dipolyhydroxystearate (Dehymuls® PGPH), Polyglycerin-3-Diisostearate (Lameform® TGI), Polyglyceryl-4 Isostearate (Isolan® GI 34), Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-3 Diisostearate (Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450), Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010/90), Polyglyceryl-3 Cetyl Ether (Chimexane® NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) und Polyglyceryl Polyricinoleate (Admul® WOL 1403) Polyglyceryl Dimerate Isostearate sowie deren Gemische. Beispiele für weitere geeignete Polyolester sind die gegebenenfalls mit 1 bis 30 Mol Ethylenoxid umgesetzten Mono-, Di- und Triester von Trimethylolpropan oder Pentaerythrit mit Laurinsäure, Kokosfettsäure, Talgfettsäure, Palmitinsäure, Stearinsäure, Ölsäure, Behensäure und dergleichen.Typical examples of suitable polyglycerol esters are polyglyceryl-2 dipolyhydroxystearates (Dehymuls® PGPH), polyglycerol-3-diisostearate (Lameform® TGI), polyglyceryl-4 Isostearate (Isolan® GI 34), polyglyceryl-3 oleates, diisostearoyl polyglyceryl-3 Diisostearate (Isolan® PDI), polyglyceryl-3 methylglucose distearate (Tego Care® 450), Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010 / 90), Polyglyceryl-3 Cetyl Ether (Chimexane® NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and Polyglyceryl Polyricinoleate (Admul® WOL 1403) Polyglyceryl Dimerate isostearates and their mixtures. Examples of other suitable polyol esters are the mono-, di- and optionally reacted with 1 to 30 mol ethylene oxide Triester of trimethylolpropane or pentaerythritol with lauric acid, coconut fatty acid, Tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like.
Typische anionische Emulgatoren sind aliphatische Fettsäuren mit 12 bis 22 Kohlenstoffatomen, wie beispielsweise Palmitinsäure, Stearinsäure oder Behensäure, sowie Dicarbonsäuren mit 12 bis 22 Kohlenstoffatomen, wie beispielsweise Azelainsäure oder Sebacinsäure.Typical anionic emulsifiers are aliphatic fatty acids with 12 to 22 carbon atoms, such as palmitic acid, stearic acid or behenic acid, and dicarboxylic acids with 12 to 22 carbon atoms, such as azelaic acid or Sebacic acid.
Weiterhin können als Emulgatoren zwitterionische Tenside verwendet werden. Als zwitterionische Tenside werden solche oberflächenaktiven Verbindungen bezeichnet, die im Molekül mindestens eine quartäre Ammoniumgruppe und mindestens eine Carboxylatund eine Sulfonatgruppe tragen. Besonders geeignete zwitterionische Tenside sind die sogenannten Betaine wie die N-Alkyl-N,N-dimethylammoniumglycinate, beispielsweise das Kokosalkyldimethylammoniumglycinat, N-Acylaminopropyl-N,N-dimethylammoniumglycinate, beispielsweise das Kokosacylaminopropyldimethyl-ammoniumglycinat, und 2-Alkyl-3-carboxylmethyl-3-hydroxyethylimidazoline mit jeweils 8 bis 18 C-Atomen in der Alkyl- oder Acylgruppe sowie das Kokosacylaminoethylhydroxyethylcarboxymethylglycinat. Besonders bevorzugt ist das unter der CTFA-Bezeichnung Cocamidopropyl Betaine bekannte Fettsäureamid-Derivat. Ebenfalls geeignete Emulgatoren sind ampholytische Tenside. Unter ampholytischen Tensiden werden solche oberflächenaktiven Verbindungen verstanden, die außer einer C8/18-Alkyl- oder Acylgruppe im Molekül mindestens eine freie Aminogruppe und mindestens eine -COOH- oder -SO3H-Gruppe enthalten und zur Ausbildung innerer Salze befähigt sind. Beispiele für geeignete ampholytische Tenside sind N-Alkylglycine, N-Alkylpropionsäuren, N-Alkylaminobuttersäuren, N-Alkyliminodipropionsäuren, N-Hydroxyethyl-N-alkylamidopropylglycine, N-Alkyltaurine, N-Alkyl-sarcosine, 2-Alkylaminopropionsäuren und Alkylaminoessigsäuren mit jeweils etwa 8 bis 18 C-Atomen in der Alkylgruppe. Besonders bevorzugte ampholytische Tenside sind das N-Kokosalkylaminopropionat, das Kokosacylaminoethylaminopropionat und das C12/18-Acylsarcosin. Schließlich kommen auch Kationtenside als Emulgatoren in Betracht, wobei solche vom Typ der Esterquats, vorzugsweise methylquaternierte Difettsäuretriethanolaminester-Salze, besonders bevorzugt sind.Zwitterionic surfactants can also be used as emulsifiers. Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example coconut acylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxylm -hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. The fatty acid amide derivative known under the CTFA name of Cocamidopropyl Betaine is particularly preferred. Suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C 8/18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO 3 H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C 12/18 acylsarcosine. Finally, cationic surfactants are also suitable as emulsifiers, those of the esterquat type, preferably methylquaternized difatty acid triethanolamine ester salts, being particularly preferred.
In der Regel werden die Emulgatoren in solchen Mengen eingesetzt, dass ihr Anteil an den fertigen Mikrokapseln 0,1 bis 5, vorzugsweise 0,25 bis 2 und insbesondere 0,5 bis 1 Gew.-% beträgt.As a rule, the emulsifiers are used in such quantities that their share in the produce microcapsules 0.1 to 5, preferably 0.25 to 2 and in particular 0.5 to 1% by weight is.
Chitosane stellen Biopolymere dar und werden zur Gruppe der Hydrokolloide gezählt. Chemisch betrachtet handelt es sich um partiell deacetylierte Chitine unterschiedlichen Molekulargewichtes, die den folgenden - idealisierten - Monomerbaustein enthalten: Chitosans are biopolymers and belong to the group of hydrocolloids. From a chemical point of view, these are partially deacetylated chitins of different molecular weights that contain the following - idealized - monomer unit:
Im Gegensatz zu den meisten Hydrokolloiden, die im Bereich biologischer pH-Werte negativ geladen sind, stellen Chitosane unter diesen Bedingungen kationische Biopolymere dar. Die positiv geladenen Chitosane können mit entgegengesetzt geladenen Oberflächen in Wechselwirkung treten und werden daher in kosmetischen Haar- und Körperpflegemitteln sowie pharmazeutischen Zubereitungen eingesetzt (vgl. Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A6, Weinheim, Verlag Chemie, 1986, S. 231-232). Übersichten zu diesem Thema sind auch beispielsweise von B. Gesslein et al. in HAPPI 27, 57 (1990), O. Skaugrud in Drug Cosm.Ind. 148, 24 (1991) und E. Onsoyen et al. in Seifen-Öle-Fette-Wachse 117, 633 (1991) erschienen. Zur Herstellung der Chitosane geht man von Chitin, vorzugsweise den Schalenresten von Krustentieren aus, die als billige Rohstoffe in großen Mengen zur Verfügung stehen. Das Chitin wird dabei in einem Verfahren, das erstmals von Hackmann et al. beschrieben worden ist, üblicherweise zunächst durch Zusatz von Basen deproteiniert, durch Zugabe von Mineralsäuren demineralisiert und schließlich durch Zugabe von starken Basen deacetyliert, wobei die Molekulargewichte über ein breites Spektrum verteilt sein können. Entsprechende Verfahren sind beispielsweise aus Makromol. Chem. 177, 3589 (1976) oder der französischen Patentanmeldung FR 2701266 A bekannt. Vorzugsweise werden solche Typen eingesetzt, wie sie in den deutschen Patentanmeldungen DE 4442987 A1 und DE 19537001 A1 (Henkel) offenbart werden und die ein durchschnittliches Molekulargewicht von 10.000 bis 500.000 bzw. 800.000 bis 1.200.000 Dalton aufweisen und/oder eine Viskosität nach Brookfield (1 Gew.- %ig in Glycolsäure) unterhalb von 5000 mPas, einen Deacetylierungsgrad im Bereich von 80 bis 88 % und einem Aschegehalt von weniger als 0,3 Gew.-% besitzen. Aus Gründen der besseren Wasserlöslichkeit werden die Chitosane in der Regel in Form ihrer Salze, vorzugsweise als Glycolate eingesetzt. In der Regel werden die Chitosane in solchen Mengen eingesetzt, dass ihr Anteil an den fertigen Mikrokapseln 5 bis 30, vorzugsweise 10 bis 25 und insbesondere 15 bis 20 Gew.-% beträgt.In contrast to most hydrocolloids, which are negatively charged in the range of biological pH values, chitosans are cationic biopolymers under these conditions. The positively charged chitosans can interact with oppositely charged surfaces and are therefore used in cosmetic hair and body care products and pharmaceuticals Preparations used (cf. Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A6, Weinheim, Verlag Chemie, 1986, pp. 231-232). Overviews on this topic are also available, for example, from B. Gesslein et al. in HAPPI 27 , 57 (1990), O. Skaugrud in Drug Cosm. Ind. 148: 24 (1991) and E. Onsoyen et al. in Seifen-Öle-Fette-Wwachs 117 , 633 (1991) . The production of chitosans is based on chitin, preferably the shell remains of crustaceans, which are available in large quantities as cheap raw materials. The chitin is used in a process that was first developed by Hackmann et al. has been described, usually first deproteinized by adding bases, demineralized by adding mineral acids and finally deacetylated by adding strong bases, it being possible for the molecular weights to be distributed over a broad spectrum. Appropriate methods are, for example, made from Makromol. Chem. 177 , 3589 (1976) or French patent application FR 2701266 A. Such types are preferably used as are disclosed in German patent applications DE 4442987 A1 and DE 19537001 A1 (Henkel) and which have an average molecular weight of 10,000 to 500,000 or 800,000 to 1,200,000 Daltons and / or a Brookfield viscosity ( 1% by weight in glycolic acid) below 5000 mPas, a degree of deacetylation in the range from 80 to 88% and an ash content of less than 0.3% by weight. For reasons of better water solubility, the chitosans are generally used in the form of their salts, preferably as glycolates. As a rule, the chitosans are used in amounts such that their share in the finished microcapsules is 5 to 30, preferably 10 to 25 and in particular 15 to 20% by weight.
Für die Bildung der äußeren Hülle eignen sich Homo- und Copolymere der Acryl- und/oder Methacrylsäure, die beispielsweise ein Molekulargewicht von 1.000 bis 200.000, vorzugsweise 5.000 bis 100.000 und insbesondere 10.000 bis 50.000 Dalton aufweisen und gegebenenfalls vernetzt vorliegen. Typische Beispiel für geeignete Handelsprodukte sind die Carbopole® und Pemulen-Typen von Goodrich, Synthalene® von Sigma, Keltrol-Typen von Kelco, Sepigel-Typen von Seppic sowie Salcare-Typen von Allied Colloids. Besonders bevorzugt ist der Einsatz des Produktes Carbopol® ETD 2020 von Goodrich, eines C10-C30-alkylvernetzten Polyacrylats. In der Regel werden die Poly(meth)acrylate in solchen Mengen eingesetzt, dass ihr Anteil an den fertigen Mikrokapseln 5 bis 30, vorzugsweise 10 bis 25 und insbesondere 15 bis 20 Gew.-% beträgt.For the formation of the outer shell, homo- and copolymers of acrylic and / or methacrylic acid are suitable which, for example, have a molecular weight of 1,000 to 200,000, preferably 5,000 to 100,000 and in particular 10,000 to 50,000 Daltons and are optionally crosslinked. Typical examples of suitable commercial products are the Carbopole® and Pemulen types from Goodrich, Synthalene® from Sigma, Keltrol types from Kelco, Sepigel types from Seppic and Salcare types from Allied Colloids. It is particularly preferred to use the Carbopol® ETD 2020 product from Goodrich, a C 10 -C 30 alkyl-crosslinked polyacrylate. As a rule, the poly (meth) acrylates are used in amounts such that their proportion in the finished microcapsules is 5 to 30, preferably 10 to 25 and in particular 15 to 20% by weight.
Zur Herstellung der neuen Mikrokapseln stellt man üblicherweise zunächst eine erste wässrige Carboxymethylcelluloselösung, welche weitere Zusatzstoffe, wie z.B. Konservierungsmittel und Antioxidantien enthalten kann und ivorzugsweise sauer, beispielsweise auf einen pH-Wert im Bereich von 2 bis 5 eingestellt ist. Parallel wird eine wässrige Lösung oder Dispersion des Wirkstoffes hergestellt. In beiden Zubereitungen - oder auch nur in einer von ihnen - können Emulgatoren enthalten sein, welche die Aufgaben haben, bei der folgenden Mischung die Bildung der Emulsion, bei der es sich in der Regel um eine O/W-Emulsion handelt, zu fördern. Diese Emulsion - auch als Matrix bezeichnet - wird nun tropfenweise und unter starker Scherung mit der wässrigen Lösung des Chitosansalzes in Kontakt gebracht, wobei die innere Hülle gebildet und der Wirkstoff verkapselt wird. Anschließend wird die wässrige Zubereitung mit einer Poly(meth)acrylatlösung versetzt, wobei die freien Amingruppen des Chitosans dann mit den anionischen Gruppen des Polymers abreagieren, wodurch dann die äußere Hülle geformt wird. Alternativ können die Poly(meth)acrylate auch im ersten Schritt zur Bildung der inneren Hülle dienen und die Alginate bzw. Carboxymethylcellulose dann zur Ausformung der äußeren Hülle eingesetzt werden. Hierzu bedarf es im wesentlichen nur des molaren Austausches der beiden Polymertypen. Grundsätzlich ist es weiter möglich, die so entstandenen Mikrokapseln mit doppelter Hülle aufs neue mit wäßriger Chitosanlösung zu versetzen, um eine dritte Hülle herzustellen.To produce the new microcapsules, a first aqueous solution is usually first prepared Carboxymethyl cellulose solution, which further additives, e.g. preservative and may contain antioxidants and preferably acidic, for example to a pH is set in the range from 2 to 5. In parallel, an aqueous solution or dispersion of the active ingredient. In both preparations - or even in one of them - Emulsifiers, which have the functions, can be contained in the following mixture the formation of the emulsion, which is usually an O / W emulsion, to promote. This emulsion - also known as the matrix - is now added dropwise and brought into contact with the aqueous solution of the chitosan salt under strong shear, forming the inner shell and encapsulating the active ingredient. Then the aqueous preparation with a poly (meth) acrylate solution, the free amine groups of the chitosan then react with the anionic groups of the polymer, whereby then the outer shell is molded. Alternatively, the poly (meth) acrylates can also be used in the first step is to form the inner shell and the alginates or carboxymethyl cellulose then be used to form the outer shell. This essentially requires only the molar exchange of the two types of polymer. Basically, it is further possible, the resulting microcapsules with a double shell again with aqueous Add chitosan solution to make a third shell.
Weitere Gegenstände der Erfindung betreffen die Verwendung der Mikrokapseln zur Herstellung von kosmetischen bzw. pharmazeutischen Zubereitungen sowie textilen Flächengebilden, wie Garnen, Fasern oder entsprechenden Endprodukten, die die Kapseln in Mengen von 0,1 bis 15, vorzugsweise 1 bis 10 und insbesondere 3 bis 8 Gew.-% enthalten können.Further objects of the invention relate to the use of the microcapsules for the production of cosmetic or pharmaceutical preparations as well as textile fabrics, such as yarns, fibers or corresponding end products, which the capsules in quantities from 0.1 to 15, preferably 1 to 10 and in particular 3 to 8% by weight.
Die erfindungsgemäßen Mikrokapseln können zur Herstellung von kosmetischen und/oder pharmazeutischen Zubereitungen, wie beispielsweise Haarshampoos, Haarlotionen, Schaumbäder, Duschbäder, Cremes, Gele, Lotionen, alkoholischen und wässrig/alkoholischen Lösungen, Emulsionen, Wachs/ Fett-Massen, Stiftpräparaten, Pudern oder Salben dienen. Diese Mittel können ferner als weitere Hilfs- und Zusatzstoffe milde Tenside, Ölkörper, Emulgatoren, Perlglanzwachse, Konsistenzgeber, Verdickungsmittel, Überfettungsmittel, Stabilisatoren, Polymere, Siliconverbindungen, Fette, Wachse, Lecithine, Phospholipide, biogene Wirkstoffe, UV-Lichtschutzfaktoren, Antioxidantien, Deodorantien, Antitranspirantien, Antischuppenmittel, Filmbildner, Quellmittel, Insektenrepellentien, Selbstbräuner, Tyrosininhibitoren (Depigmentierungsmittel), Hydrotrope, Solubilisatoren, Konservierungsmittel, Parfümöle, Farbstoffe und dergleichen enthalten. Die entsprechenden Zusatzstoffe sind bereits in den Kapiteln Wirkstoffe/Emulgatoren erläutert worden, so dass auf eine Wiederholung an dieser Stelle verzichtet werden kann. The microcapsules according to the invention can be used for the production of cosmetic and / or pharmaceutical preparations, such as hair shampoos, hair lotions, Bubble baths, shower baths, creams, gels, lotions, alcoholic and aqueous / alcoholic Solutions, emulsions, wax / fat masses, stick preparations, powders or Serve ointments. These agents can also be used as further auxiliaries and additives, mild surfactants, Oil bodies, emulsifiers, pearlescent waxes, consistency agents, thickeners, superfatting agents, Stabilizers, polymers, silicone compounds, fats, waxes, lecithins, Phospholipids, biogenic agents, UV light protection factors, antioxidants, deodorants, Antiperspirants, antidandruff agents, film formers, swelling agents, insect repellents, Self-tanners, tyrosine inhibitors (depigmenting agents), hydrotropes, solubilizers, Contain preservatives, perfume oils, dyes and the like. The corresponding Additives have already been explained in the chapters on active ingredients / emulsifiers, so that repetition at this point can be dispensed with.
Die erfindungsgemäßen Mikrokapseln können analog zum Einsatz bei natürlichen Keratinfasern auch zur Ausrüstung von Textilien dienen, obschon hier der Schwerpunkt in der Verbesserung des Flammschutzes liegt. In gleicher Weise können die Garne ausgerüstet werden, indem man die Mikrokapseln beispielsweise als Bestandteile von Spulölen oder Spinnfaserpräparationen aufbringt. Demzufolge eignen sich die Mikrokapseln zur Ausrüstung aller textiler Flächengebilde. In einer besonderen Ausführungsform der vorliegenden Erfindung enthalten die Mikrokapseln neben den Flammschutzmitteln noch fettlösliche Farbstoffe, wie beispielsweise Beta-Carotine oder Tocopherole, die dann als Indikatoren dafür dienen können, dass die Kapseln vom Gewebe aufgenommen worden sind. The microcapsules according to the invention can be used analogously to natural keratin fibers also serve to finish textiles, although the focus here is on improvement of the flame retardant. The yarns can be finished in the same way by using the microcapsules, for example, as components of winding oils or spin fiber preparations applies. As a result, the microcapsules are suitable for equipping everyone textile fabrics. In a particular embodiment of the present invention In addition to the flame retardants, the microcapsules also contain fat-soluble dyes, such as for example beta-carotenes or tocopherols, which can then serve as indicators for that the capsules have been absorbed by the tissue.
Alle Mengenangaben in den folgenden Beispielen beziehen sich auf die Zusammensetzung des Endproduktes; die Differenz zu 100 Gew.-% wird durch den Wasseranteil gebildet.All quantities in the following examples relate to the composition of the final product; the difference to 100% by weight is formed by the water content.
Beispiel 1. In einem ersten Reaktionsgefäß wurden 0,5 Gew.-% Konservierungsmittel (Phenonip®) und 25 Gew.-% Carboxymethylcellulose in Wasser dispergiert und auf einen pH-Wert von 3,5 eingestellt. In einem zweiten Gefäß wurde eine Mischung von 10 Gew.-% Retinol, 0,25 Gew.-% Sorbitanmonolaurat+20EO (Eumulgin® SML20), 0,25 Gew.-% Sorbitanmonooleat (Dehymuls® SMO) und 1 Gew.-% BHT hergestellt und der ersten Mischung zugegeben, wobei eine O/W-Emulsion entstand. Unter Rühren wurde die Emulsion tropfenweise mit einer 20 Gew.-%igen wässrigen Lösung von Chitosanglycolat (Hydagen® CMF) versetzt, wobei sich durch Reaktion des Chitosans mit der Carboxymethylcellulose eine erste Kapselhülle bildete. Anschließend wurde eine 3 Gew.-%ige Polyacrylatlösung (Carbopol® ETD 2020, Fa.Goodrich) hergestellt und in einer Menge von 20 Gew.-% der Zubereitung mit den ersten Mikrokapseln zugesetzt, wobei sich durch Reaktion des Polyacrylats mit den freien Aminogruppen des Chitosans eine zweite Hülle bildet. Der Mikrokapselgehalt der Zubereitung betrug ca. 80 Gew.-% Example 1. In a first reaction vessel, 0.5% by weight of preservative (Phenonip®) and 25% by weight of carboxymethyl cellulose were dispersed in water and adjusted to a pH of 3.5. A mixture of 10% by weight retinol, 0.25% by weight sorbitan monolaurate + 20EO (Eumulgin® SML20), 0.25% by weight sorbitan monooleate (Dehymuls® SMO) and 1% by weight was mixed in a second vessel. BHT produced and added to the first mixture, whereby an O / W emulsion was formed. A 20% by weight aqueous solution of chitosan glycolate (Hydagen® CMF) was added dropwise to the emulsion with stirring, a first capsule shell being formed by reaction of the chitosan with the carboxymethyl cellulose. A 3% by weight polyacrylate solution (Carbopol® ETD 2020, from Goodrich) was then prepared and added in an amount of 20% by weight to the preparation with the first microcapsules, the reaction of the polyacrylate with the free amino groups of the Chitosans forms a second shell. The microcapsule content of the preparation was approx. 80% by weight
Beispiel 2. In einem ersten Reaktionsgefäß wurden 0,5 Gew.-% Konservierungsmittel (Phenonip®) und 25 Gew.-% Natriumalginat in Wasser dispergiert und auf einen pH-Wert von 3,5 eingestellt. In einem zweiten Gefäß wurde eine Mischung von 10 Gew.-% Panthenol, 20 Gew.-% Sorbitanmonolaurat+20EO (Eumulgin® SML20), 0,25 Gew.-% Cetearyl Glucosides und 1 Gew.-% BHT hergestellt und der ersten Mischung zugegeben, wobei eine O/W-Emulsion entstand. Unter Rühren wurde die Emulsion tropfenweise mit einer 20 Gew.-%igen wässrigen Lösung von Chitosanglycolat (Hydagen® CMF) versetzt, wobei sich durch Reaktion des Chitosans mit der Carboxymethylcellulose eine erste Kapselhülle bildete. Anschließend wurde eine 3 Gew.-%ige Polyacrylatlösung (Carbopol® ETD 2020, Fa.Goodrich) hergestellt und in einer Menge von 20 Gew.-% der Zubereitung mit den ersten Mikrokapseln zugesetzt, wobei sich durch Reaktion des Polyacrylats mit den freien Aminogruppen des Chitosans eine zweite Hülle bildet. Der Mikrokapselgehalt der Zubereitung betrug ca. 80 Gew.-% Example 2. In a first reaction vessel, 0.5% by weight of preservative (Phenonip®) and 25% by weight of sodium alginate were dispersed in water and adjusted to a pH of 3.5. A mixture of 10% by weight panthenol, 20% by weight sorbitan monolaurate + 20EO (Eumulgin® SML20), 0.25% by weight cetearyl glucosides and 1% by weight BHT and the first mixture was prepared in a second vessel added, resulting in an O / W emulsion. A 20% by weight aqueous solution of chitosan glycolate (Hydagen® CMF) was added dropwise to the emulsion with stirring, a first capsule shell being formed by reaction of the chitosan with the carboxymethyl cellulose. A 3% by weight polyacrylate solution (Carbopol® ETD 2020, from Goodrich) was then prepared and added in an amount of 20% by weight to the preparation with the first microcapsules, the reaction of the polyacrylate with the free amino groups of the Chitosans forms a second shell. The microcapsule content of the preparation was approx. 80% by weight
Beispiel 3. In einem ersten Reaktionsgefäß wurden 0,5 Gew.-% Konservierungsmittel (Phenonip®) und 25 Gew.-% Polyacrylat (Carbopol® ETD 2020, Fa.Goodrich) in Wasser dispergiert und auf einen pH-Wert von 3,5 eingestellt. In einem zweiten Gefäß wurde eine Mischung von 10 Gew.-% Retinol, 0,25 Gew.-% Sorbitanmonolaurat+20EO (Eumulgin® SML20), 0,25 Gew.-% Sorbitanmonooleat (Dehymuls® SMO) und 1 Gew.-% BHT hergestellt und der ersten Mischung zugegeben, wobei eine O/W-Emulsion entstand. Unter Rühren wurde die Emulsion tropfenweise mit einer 20 Gew.-%igen wässrigen Lösung von Chitosanglycolat (Hydagen® CMF) versetzt, wobei sich durch Reaktion des Chitosans mit dem Polyacrylat eine erste Kapselhülle bildete. Anschließend wurde eine 1 Gew.-%ige Carboxymethylcelluloselösung hergestellt und in einer Menge von 20 Gew.-% der Zubereitung mit den ersten Mikrokapseln zugesetzt, wobei sich durch Reaktion des CMC mit den freien Aminogruppen des Chitosans eine zweite Hülle bildet. Der Mikrokapselgehalt der Zubereitung betrug ca. 80 Gew.-% Example 3. In a first reaction vessel, 0.5% by weight of preservative (Phenonip®) and 25% by weight of polyacrylate (Carbopol® ETD 2020, from Goodrich) were dispersed in water and brought to a pH of 3.5 set. A mixture of 10% by weight retinol, 0.25% by weight sorbitan monolaurate + 20EO (Eumulgin® SML20), 0.25% by weight sorbitan monooleate (Dehymuls® SMO) and 1% by weight was mixed in a second vessel. BHT produced and added to the first mixture, whereby an O / W emulsion was formed. A 20% by weight aqueous solution of chitosan glycolate (Hydagen® CMF) was added dropwise to the emulsion with stirring, a first capsule shell being formed by reaction of the chitosan with the polyacrylate. A 1% by weight carboxymethyl cellulose solution was then prepared and added in an amount of 20% by weight to the preparation with the first microcapsules, a second shell being formed by reaction of the CMC with the free amino groups of the chitosan. The microcapsule content of the preparation was approx. 80% by weight
Formulierungsbeispiele sind der nachstehenden Tabelle 1 zu entnehmen.
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WO2004016234A1 (en) * | 2002-08-14 | 2004-02-26 | Quest International Services B.V. | Compositions comprising encapsulated material |
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EP1254983B1 (en) * | 2001-04-30 | 2004-09-01 | Cognis Iberia, S.L. | Use of microcapsules (XIV) |
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